From 83572a0b22e13dcc50ec3e9990fec07db889082a Mon Sep 17 00:00:00 2001 From: Alon Grinberg Dana Date: Mon, 19 Aug 2024 08:36:01 +0300 Subject: [PATCH 01/16] Added parser parse_active_space() --- arc/parser.py | 75 ++++++++++++++++++++++++++++++++++++++++++++++++++- 1 file changed, 74 insertions(+), 1 deletion(-) diff --git a/arc/parser.py b/arc/parser.py index 028d5e9405..86c117bffa 100644 --- a/arc/parser.py +++ b/arc/parser.py @@ -4,7 +4,7 @@ import os import re -from typing import Dict, List, Match, Optional, Tuple, Union +from typing import TYPE_CHECKING, Dict, List, Match, Optional, Tuple, Union import numpy as np import pandas as pd @@ -18,6 +18,8 @@ from arc.exceptions import InputError, ParserError from arc.species.converter import hartree_to_si, str_to_xyz, xyz_from_data +if TYPE_CHECKING: + from arc.species.species import ARCSpecies logger = get_logger() @@ -1262,3 +1264,74 @@ def parse_scan_conformers(file_path: str) -> pd.DataFrame: if not red_ind.empty: scan_conformers.drop(red_ind, inplace=True) return scan_conformers + + +def parse_active_space(sp_path: str, species: 'ARCSpecies') -> Dict[str, Union[List[int], Tuple[int, int]]]: + """ + Parse the active space (electrons and orbitals) from a Molpro CCSD output file. + + Args: + sp_path (str): The path to the sp job output file. + species ('ARCSpecies'): The species to consider. + + Returns: + Dict[str, Union[List[int], Tuple[int, int]]]: + The active orbitals. Possible keys are: + 'occ' (List[int]): The occupied orbitals. + 'closed' (List[int]): The closed-shell orbitals. + 'frozen' (List[int]): The frozen orbitals. + 'core' (List[int]): The core orbitals. + 'e_o' (Tuple[int, int]): The number of active electrons, determined by the total number + of electrons minus the core electrons (2 e's per heavy atom), and the number of active + orbitals, determined by the number of closed-shell orbitals and active orbitals + (w/o core orbitals). + """ + if not os.path.isfile(sp_path): + raise InputError(f'Could not find file {sp_path}') + active = dict() + num_heavy_atoms = sum([1 for symbol in species.get_xyz()['symbols'] if symbol not in ['H', 'D', 'T']]) + nuclear_charge, total_closed_shell_orbitals, total_active_orbitals = None, None, None + core_orbitals, closed_shell_orbitals, active_orbitals = None, None, None + with open(sp_path, 'r') as f: + lines = f.readlines() + for line in lines: + if 'NUCLEAR CHARGE:' in line: + # NUCLEAR CHARGE: 32 + nuclear_charge = int(line.split()[-1]) + if 'Number of core orbitals:' in line: + # Number of core orbitals: 1 ( 1 0 0 0 0 0 0 0 ) + # Number of core orbitals: 3 ( 3 ) + core_orbitals = line.split('(')[-1].split(')')[0].split() + if 'Number of closed-shell orbitals:' in line: + # Number of closed-shell orbitals: 11 ( 9 2 ) + # Number of closed-shell orbitals: 8 ( 8 ) + closed_shell_orbitals = line.split('(')[-1].split(')')[0].split() + total_closed_shell_orbitals = int(line.split('(')[0].split()[-1]) + if 'Number of active' in line and 'orbitals' in line: + # Number of active orbitals: 2 ( 1 1 ) + # Number of active orbitals: 2 ( 2 ) + active_orbitals = line.split('(')[-1].split(')')[0].split() + total_active_orbitals = int(line.split('(')[0].split()[-1]) + if None not in [nuclear_charge, total_closed_shell_orbitals, total_active_orbitals, + core_orbitals, closed_shell_orbitals, active_orbitals]: + break + active_space_electrons = nuclear_charge - species.charge - 2 * num_heavy_atoms + if (total_closed_shell_orbitals is None) ^ (total_active_orbitals is None): + num_active_space_orbitals = total_closed_shell_orbitals or total_active_orbitals + else: + num_active_space_orbitals = total_closed_shell_orbitals + total_active_orbitals + active['e_o'] = (active_space_electrons, num_active_space_orbitals) + if core_orbitals is not None: + active['occ'] = [int(c) for c in core_orbitals] + if closed_shell_orbitals is not None: + active['closed'] = [int(c) for c in closed_shell_orbitals] + for i in range(len(closed_shell_orbitals)): + active['occ'][i] += int(closed_shell_orbitals[i]) + if active_orbitals is not None: + active['occ'][i] += int(active_orbitals[i]) + if active_orbitals is not None and int(active_orbitals[0]) == 0: + # No 1st irrep is suggested to be active. + # We should therefore add another active orbital to the 1st irrep. + active['occ'][0] += 1 + + return active From 2ef272e2eb77f4cb63a40770765ab4d44d4d5069 Mon Sep 17 00:00:00 2001 From: Alon Grinberg Dana Date: Mon, 19 Aug 2024 08:56:19 +0300 Subject: [PATCH 02/16] Tests: parse active space --- arc/parser_test.py | 33 ++ arc/testing/sp/H_CCSD.out | 319 +++++++++++++++ arc/testing/sp/N_CCSD.out | 340 ++++++++++++++++ arc/testing/sp/ONHO(T)_sp_CCSD(T).out | 546 ++++++++++++++++++++++++++ arc/testing/sp/TS_x118_sp_CCSD(T).out | 531 +++++++++++++++++++++++++ 5 files changed, 1769 insertions(+) create mode 100644 arc/testing/sp/H_CCSD.out create mode 100644 arc/testing/sp/N_CCSD.out create mode 100644 arc/testing/sp/ONHO(T)_sp_CCSD(T).out create mode 100644 arc/testing/sp/TS_x118_sp_CCSD(T).out diff --git a/arc/parser_test.py b/arc/parser_test.py index 2643cb2e9d..6748e53d1b 100644 --- a/arc/parser_test.py +++ b/arc/parser_test.py @@ -719,6 +719,39 @@ def test_parse_conformers(self): self.assertEqual(expected_conf_18, scan_conformers[18].to_list()) self.assertEqual(expected_conf_36, scan_conformers[36].to_list()) + def test_parse_active_space(self): + """Test parsing active space information""" + path = os.path.join(ARC_PATH, 'arc', 'testing', 'sp', 'mehylamine_CCSD(T).out') + active = parser.parse_active_space(sp_path=path, + species=ARCSpecies(label='mehylamine', smiles='CN')) + self.assertEqual(active, {'e_o': (14, 7), 'occ': [7, 2], 'closed': [5, 2]}) + + path = os.path.join(ARC_PATH, 'arc', 'testing', 'sp', 'H_CCSD.out') + active = parser.parse_active_space(sp_path=path, + species=ARCSpecies(label='H', smiles='[H]')) + self.assertEqual(active, {'e_o': (1, 1)}) + + path = os.path.join(ARC_PATH, 'arc', 'testing', 'sp', 'ONHO(T)_sp_CCSD(T).out') + active = parser.parse_active_space(sp_path=path, + species=ARCSpecies(label='ONHO', smiles='[O]N[O]')) + self.assertEqual(active, {'e_o': (18, 10), 'occ': [13], 'closed': [8]}) + + path = os.path.join(ARC_PATH, 'arc', 'testing', 'sp', 'TS_x118_sp_CCSD(T).out') + active = parser.parse_active_space(sp_path=path, + species=ARCSpecies(label='x118', is_ts=True, + xyz="""N -0.0 -1.36720300 0.15499300 + O -0.0 -1.10333100 -0.98685800 + H -0.0 -0.28110100 0.76732400 + O 0.0 0.97476200 0.91364300 + O 0.0 1.44007500 -0.27062400""")) + self.assertEqual(active, {'e_o': (24, 13), 'occ': [14, 3], 'closed': [9, 2]}) + + path = os.path.join(ARC_PATH, 'arc', 'testing', 'sp', 'N_CCSD.out') + active = parser.parse_active_space(sp_path=path, + species=ARCSpecies(label='N', is_ts=False, + xyz="""N 0.0 0.0 0.0""")) + self.assertEqual(active, {'e_o': (5, 4), 'occ': [3, 1, 1, 0, 1, 0, 0, 0], 'closed': [1, 0, 0, 0, 0, 0, 0, 0]}) + if __name__ == '__main__': unittest.main(testRunner=unittest.TextTestRunner(verbosity=2)) diff --git a/arc/testing/sp/H_CCSD.out b/arc/testing/sp/H_CCSD.out new file mode 100644 index 0000000000..7aae8705f4 --- /dev/null +++ b/arc/testing/sp/H_CCSD.out @@ -0,0 +1,319 @@ + + Working directory : /gtmp/molpro.ktUcYWm4qU/ + Global scratch directory : /gtmp/molpro.ktUcYWm4qU/ + Wavefunction directory : /home/alon/wfu/ + Main file repository : /gtmp/molpro.ktUcYWm4qU/ + + id : dana + + Nodes nprocs + n131 16 + GA implementation: MPI file + GA implementation (serial work in mppx): MPI file + + Using customized tuning parameters: mindgm=1; mindgv=20; mindgc=4; mindgr=1; noblas=0; minvec=7 + default implementation of scratch files=sf + + + Variables initialized (1025), CPU time= 0.04 sec + ***,H + memory,Total=6250,m; + + geometry={angstrom; + H 0.00000000 0.00000000 0.00000000} + + gprint,orbitals; + + basis=cc-pvdz + + + + int; + + {hf; + maxit,999; + wf,spin=1,charge=0; + } + + uccsd; + + + + Commands initialized (840), CPU time= 0.02 sec, 684 directives. + Default parameters read. Elapsed time= 0.16 sec + + Checking input... + Passed +1 + + + *** PROGRAM SYSTEM MOLPRO *** + Copyright, TTI GmbH Stuttgart, 2015 + Version 2022.3 linked Wed Nov 30 13:40:34 2022 + + + ********************************************************************************************************************************** + LABEL * H + 64 bit mpp version DATE: 03-Oct-24 TIME: 23:00:14 + ********************************************************************************************************************************** + + SHA1: e31ec9a5ea85254ab76f59d122cbdd51c71cf98b + ********************************************************************************************************************************** + + Memory per process: 293 MW + Total memory per node: 6250 MW + Total GA space: 1563 MW + + GA preallocation enabled + GA check enabled + + Variable memory set to 293.0 MW + + + Geometry recognized as XYZ + + + SETTING BASIS = CC-PVDZ + + + Using spherical harmonics + + Library entry H S cc-pVDZ selected for orbital group 1 + Library entry H P cc-pVDZ selected for orbital group 1 + + + PROGRAM * SEWARD (Integral evaluation for generally contracted gaussian basis sets) Author: Roland Lindh, 1990 + + Geometry written to block 1 of record 700 + + Orientation using atomic masses + Molecule type: Atom + Symmetry elements: X,Y,Z + Rotational constants: 0.0000000 0.0000000 0.0000000 GHz (calculated with average atomic masses) + + Point group D2h + + + + ATOMIC COORDINATES + + NR ATOM CHARGE X Y Z + + 1 H 1.00 0.000000000 0.000000000 0.000000000 + + NUCLEAR CHARGE: 1 + NUMBER OF PRIMITIVE AOS: 7 + NUMBER OF SYMMETRY AOS: 7 + NUMBER OF CONTRACTIONS: 5 ( 2Ag + 1B3u + 1B2u + 0B1g + 1B1u + 0B2g + 0B3g + 0Au ) + NUMBER OF INNER CORE ORBITALS: 0 ( 0Ag + 0B3u + 0B2u + 0B1g + 0B1u + 0B2g + 0B3g + 0Au ) + NUMBER OF OUTER CORE ORBITALS: 0 ( 0Ag + 0B3u + 0B2u + 0B1g + 0B1u + 0B2g + 0B3g + 0Au ) + NUMBER OF VALENCE ORBITALS: 1 ( 1Ag + 0B3u + 0B2u + 0B1g + 0B1u + 0B2g + 0B3g + 0Au ) + + + NUCLEAR REPULSION ENERGY 0.00000000 + + + Allocated 98 MW GA space on the current processor, total: 1563 MW. Time: 0.00 sec + + Eigenvalues of metric + + 1 0.963E-01 0.190E+01 + 2 0.100E+01 + 3 0.100E+01 + 5 0.100E+01 + + + Contracted 2-electron integrals neglected if value below 1.0D-11 + AO integral compression algorithm 1 Integral accuracy 1.0D-11 + + 4.194 MB (compressed) written to integral file (100.0%) + + Node minimum: 0.262 MB, node maximum: 0.262 MB + + + NUMBER OF SORTED TWO-ELECTRON INTEGRALS: 0. BUFFER LENGTH: 32768 + NUMBER OF SEGMENTS: 1 SEGMENT LENGTH: 0 RECORD LENGTH: 524288 + + Memory used in sort: 0.56 MW + + SORT1 READ 61. AND WROTE 0. INTEGRALS IN 0 RECORDS. CPU TIME: 0.11 SEC, REAL TIME: 0.12 SEC + SORT2 READ 45. AND WROTE 45. INTEGRALS IN 16 RECORDS. CPU TIME: 0.00 SEC, REAL TIME: 0.00 SEC + + Node minimum: 0. Node maximum: 40. integrals + + OPERATOR DM FOR CENTER 0 COORDINATES: 0.000000 0.000000 0.000000 + + + ********************************************************************************************************************************** + DATASETS * FILE NREC LENGTH (MB) RECORD NAMES + 1 18 28.54 500 610 700 900 950 970 1000 129 960 1100 + VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S + 1400 1410 1200 1210 1080 1600 1650 1700 + T V H0 H01 AOSYM SMH MOLCAS OPER + + PROGRAMS * TOTAL INT + CPU TIMES * 0.88 0.69 + REAL TIME * 1.12 SEC + DISK USED * 28.79 MB (local), 475.87 MB (total) + GA USED * 0.00 MB (max) 0.00 MB (current) + ********************************************************************************************************************************** + + + Program * Restricted Hartree-Fock + + Orbital guess generated from atomic densities. Full valence occupancy: 1 0 0 0 0 0 0 0 + + + Initial alpha occupancy: 1 0 0 0 0 + Initial beta occupancy: 0 0 0 0 0 + + NELEC= 1 SYM=1 MS2= 1 THRE=1.0D-08 THRD=3.2D-06 THRG=3.2D-06 HFMA2=F DIIS_START=2 DIIS_MAX=10 DIIS_INCORE=F + + Level shifts: 0.00 (CLOSED) 0.00 (OPEN) 0.30 (GAP_MIN) + + ITER ETOT DE GRAD DDIFF DIIS NEXP TIME(IT) TIME(TOT) DIAG + 1 -0.49127155 -0.49127155 0.00D+00 0.25D+00 0 0 0.00 0.00 start + 2 -0.49821459 -0.00694305 0.37D-01 0.11D+00 1 0 0.00 0.00 diag2 + 3 -0.49927840 -0.00106381 0.13D-01 0.74D-01 2 0 0.00 0.00 diag2 + 4 -0.49927840 0.00000000 0.14D-16 0.00D+00 1 0 0.00 0.00 diag2 + 5 -0.49927840 0.00000000 0.14D-16 0.00D+00 0 0 0.00 0.00 diag + + Final alpha occupancy: 1 0 0 0 0 + Final beta occupancy: 0 0 0 0 0 + + !RHF STATE 1.1 Energy -0.499278403420 + RHF One-electron energy -0.499278403420 + RHF Two-electron energy -0.000000000000 + RHF Kinetic energy 0.499289639267 + RHF Nuclear energy 0.000000000000 + RHF Virial quotient -0.999977496333 + + !RHF STATE 1.1 Dipole moment 0.00000000 0.00000000 0.00000000 + Dipole moment /Debye 0.00000000 0.00000000 0.00000000 + + ELECTRON ORBITALS + ================= + + Orbital Occupation Energy Cen Mu Typ Coefficients + 1.1 1.00000 -0.49928 1 1 s 1.00000 + + + HOMO 1.1 -0.499278 = -13.5861eV + LUMO 2.1 0.572445 = 15.5770eV + LUMO-HOMO 1.071723 = 29.1631eV + + Orbitals saved in record 2100.2 + + + ********************************************************************************************************************************** + DATASETS * FILE NREC LENGTH (MB) RECORD NAMES + 1 18 28.54 500 610 700 900 950 970 1000 129 960 1100 + VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S + 1400 1410 1200 1210 1080 1600 1650 1700 + T V H0 H01 AOSYM SMH MOLCAS OPER + + 2 4 0.35 700 1000 520 2100 + GEOM BASIS MCVARS RHF + + PROGRAMS * TOTAL HF-SCF INT + CPU TIMES * 1.37 0.49 0.69 + REAL TIME * 5.35 SEC + DISK USED * 28.93 MB (local), 478.07 MB (total) + GA USED * 0.00 MB (max) 0.00 MB (current) + ********************************************************************************************************************************** + + + PROGRAM * CCSD (Unrestricted open-shell coupled cluster) Authors: C. Hampel, H.-J. Werner, 1991, M. Deegan, P.J. Knowles, 1992 + + + Convergence thresholds: THRVAR = 1.00D-08 THRDEN = 1.00D-06 + + Number of active orbitals: 1 ( 1 0 0 0 0 0 0 0 ) + Number of external orbitals: 4 ( 1 1 1 0 1 0 0 0 ) + + Number of N-1 electron functions: 1 + Number of N-2 electron functions: 0 + Number of singly external CSFs: 2 + Number of doubly external CSFs: 0 + Total number of CSFs: 2 + + Molecular orbitals read from record 2100.2 Type=RHF/CANONICAL + + Integral transformation finished. Total CPU: 0.00 sec, npass= 1 Memory used: 0.07 MW + + Starting RMP2 calculation, locsing= 0 + + ITER. SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) DIIS TIME + 1 1.00000000 -0.00000000 -0.49927840 0.00000000 -0.00000000 0.28D-33 0.00D+00 1 1 0.01 + + Norm of t1 vector: 0.00000000 S-energy: -0.00000000 T1 diagnostic: 0.00000000 + Norm of t2 vector: 0.00000000 P-energy: 0.00000000 + Alpha-Beta: 0.00000000 + Alpha-Alpha: 0.00000000 + Beta-Beta: 0.00000000 + + Spin contamination 0.00000000 + Reference energy -0.499278403420 + RHF-RMP2 correlation energy -0.000000000000 + !RHF-RMP2 energy -0.499278403420 + + Starting UCCSD calculation + + ITER. SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) DIIS TIME + 1 1.00000000 -0.00000000 -0.49927840 0.00000000 -0.00000000 0.19D-31 0.00D+00 1 1 0.01 + + Norm of t1 vector: 0.00000000 S-energy: -0.00000000 T1 diagnostic: 0.00000000 + D1 diagnostic: 0.00000000 + D2 diagnostic: 0.00000000 (internal) + Norm of t2 vector: 0.00000000 P-energy: 0.00000000 + Alpha-Beta: 0.00000000 + Alpha-Alpha: 0.00000000 + Beta-Beta: 0.00000000 + + Spin contamination 0.00000000 + + + RESULTS + ======= + + Reference energy -0.499278403420 + UCCSD singles energy -0.000000000000 + UCCSD pair energy 0.000000000000 + UCCSD correlation energy -0.000000000000 + + !RHF-UCCSD energy -0.499278403420 + + Program statistics: + + Available memory in ccsd: 292968731 + Min. memory needed in ccsd: 247 + Max. memory used in ccsd: 247 + Max. memory used in cckext: 32929 ( 1 integral passes) + Max. memory used in cckint: 65618 ( 1 integral passes) + + + + ********************************************************************************************************************************** + DATASETS * FILE NREC LENGTH (MB) RECORD NAMES + 1 18 28.54 500 610 700 900 950 970 1000 129 960 1100 + VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S + 1400 1410 1200 1210 1080 1600 1650 1700 + T V H0 H01 AOSYM SMH MOLCAS OPER + + 2 4 0.35 700 1000 520 2100 + GEOM BASIS MCVARS RHF + + PROGRAMS * TOTAL UCCSD HF-SCF INT + CPU TIMES * 1.42 0.04 0.49 0.69 + REAL TIME * 5.63 SEC + DISK USED * 28.93 MB (local), 478.07 MB (total) + SF USED * 0.00 MB + GA USED * 0.00 MB (max) 0.00 MB (current) + ********************************************************************************************************************************** + + UCCSD/cc-pVDZ energy= -0.499278403420 + + UCCSD HF-SCF + -0.49927840 -0.49927840 + ********************************************************************************************************************************** + Molpro calculation terminated diff --git a/arc/testing/sp/N_CCSD.out b/arc/testing/sp/N_CCSD.out new file mode 100644 index 0000000000..201df9f26d --- /dev/null +++ b/arc/testing/sp/N_CCSD.out @@ -0,0 +1,340 @@ + + Working directory : /gtmp/molpro.YUwB5GrZBI/ + Global scratch directory : /gtmp/molpro.YUwB5GrZBI/ + Wavefunction directory : /home/alon/wfu/ + Main file repository : /gtmp/molpro.YUwB5GrZBI/ + + id : dana + + Nodes nprocs + n134 16 + GA implementation: MPI file + GA implementation (serial work in mppx): MPI file + + Using customized tuning parameters: mindgm=1; mindgv=20; mindgc=4; mindgr=1; noblas=0; minvec=7 + default implementation of scratch files=sf + + + Variables initialized (1025), CPU time= 0.01 sec + ***,N + memory,Total=7813,m; + + geometry={angstrom; + N 0.00000000 0.00000000 0.00000000} + + gprint,orbitals; + + basis=cc-pvdz + + + + int; + {hf; + maxit,999; + wf,spin=3,charge=0;} + + uccsd; + + + + Commands initialized (840), CPU time= 0.03 sec, 684 directives. + Default parameters read. Elapsed time= 1.35 sec + + Checking input... + Passed +1 + + + *** PROGRAM SYSTEM MOLPRO *** + Copyright, TTI GmbH Stuttgart, 2015 + Version 2022.3 linked Wed Nov 30 13:40:34 2022 + + + ********************************************************************************************************************************** + LABEL * N + 64 bit mpp version DATE: 07-Sep-24 TIME: 22:47:54 + ********************************************************************************************************************************** + + SHA1: e31ec9a5ea85254ab76f59d122cbdd51c71cf98b + ********************************************************************************************************************************** + + Memory per process: 366 MW + Total memory per node: 7813 MW + Total GA space: 1953 MW + + GA preallocation enabled + GA check enabled + + Variable memory set to 366.2 MW + + + Geometry recognized as XYZ + + + SETTING BASIS = CC-PVDZ + + + Using spherical harmonics + + Library entry N S cc-pVDZ selected for orbital group 1 + Library entry N P cc-pVDZ selected for orbital group 1 + Library entry N D cc-pVDZ selected for orbital group 1 + + + PROGRAM * SEWARD (Integral evaluation for generally contracted gaussian basis sets) Author: Roland Lindh, 1990 + + Geometry written to block 1 of record 700 + + Orientation using atomic masses + Molecule type: Atom + Symmetry elements: X,Y,Z + Rotational constants: 0.0000000 0.0000000 0.0000000 GHz (calculated with average atomic masses) + + Point group D2h + + + + ATOMIC COORDINATES + + NR ATOM CHARGE X Y Z + + 1 N 7.00 0.000000000 0.000000000 0.000000000 + + NUCLEAR CHARGE: 7 + NUMBER OF PRIMITIVE AOS: 27 + NUMBER OF SYMMETRY AOS: 26 + NUMBER OF CONTRACTIONS: 14 ( 5Ag + 2B3u + 2B2u + 1B1g + 2B1u + 1B2g + 1B3g + 0Au ) + NUMBER OF INNER CORE ORBITALS: 0 ( 0Ag + 0B3u + 0B2u + 0B1g + 0B1u + 0B2g + 0B3g + 0Au ) + NUMBER OF OUTER CORE ORBITALS: 1 ( 1Ag + 0B3u + 0B2u + 0B1g + 0B1u + 0B2g + 0B3g + 0Au ) + NUMBER OF VALENCE ORBITALS: 4 ( 1Ag + 1B3u + 1B2u + 0B1g + 1B1u + 0B2g + 0B3g + 0Au ) + + + NUCLEAR REPULSION ENERGY 0.00000000 + + + Allocated 123 MW GA space on the current processor, total: 1954 MW. Time: 0.05 sec + + EXTRA SYMMETRY OF AOS IN SYMMETRY 1: 1 1 1 2 3 + + Eigenvalues of metric + + 1 0.451E-01 0.100E+01 0.100E+01 0.100E+01 0.195E+01 + 2 0.184E+00 0.182E+01 + 3 0.184E+00 0.182E+01 + 4 0.100E+01 + 5 0.184E+00 0.182E+01 + 6 0.100E+01 + 7 0.100E+01 + + + Contracted 2-electron integrals neglected if value below 1.0D-11 + AO integral compression algorithm 1 Integral accuracy 1.0D-11 + + 4.194 MB (compressed) written to integral file (100.0%) + + Node minimum: 0.262 MB, node maximum: 0.262 MB + + + NUMBER OF SORTED TWO-ELECTRON INTEGRALS: 129. BUFFER LENGTH: 32768 + NUMBER OF SEGMENTS: 1 SEGMENT LENGTH: 129 RECORD LENGTH: 524288 + + Memory used in sort: 0.56 MW + + SORT1 READ 1852. AND WROTE 126. INTEGRALS IN 1 RECORDS. CPU TIME: 0.01 SEC, REAL TIME: 0.01 SEC + SORT2 READ 968. AND WROTE 1083. INTEGRALS IN 16 RECORDS. CPU TIME: 0.00 SEC, REAL TIME: 0.00 SEC + + Node minimum: 4. Node maximum: 490. integrals + + OPERATOR DM FOR CENTER 0 COORDINATES: 0.000000 0.000000 0.000000 + + + ********************************************************************************************************************************** + DATASETS * FILE NREC LENGTH (MB) RECORD NAMES + 1 18 28.55 500 610 700 900 950 970 1000 129 960 1100 + VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S + 1400 1410 1200 1210 1080 1600 1650 1700 + T V H0 H01 AOSYM SMH MOLCAS OPER + + PROGRAMS * TOTAL INT + CPU TIMES * 0.85 0.39 + REAL TIME * 2.76 SEC + DISK USED * 28.80 MB (local), 524.87 MB (total) + GA USED * 0.00 MB (max) 0.00 MB (current) + ********************************************************************************************************************************** + + + Program * Restricted Hartree-Fock + + Orbital guess generated from atomic densities. Full valence occupancy: 2 1 1 0 1 0 0 0 + + + Initial alpha occupancy: 2 1 1 0 1 0 0 + Initial beta occupancy: 2 0 0 0 0 0 0 + + NELEC= 7 SYM=8 MS2= 3 THRE=1.0D-08 THRD=3.2D-06 THRG=3.2D-06 HFMA2=F DIIS_START=2 DIIS_MAX=10 DIIS_INCORE=F + + Level shifts: 0.00 (CLOSED) 0.00 (OPEN) 0.30 (GAP_MIN) + + ITER ETOT DE GRAD DDIFF DIIS NEXP TIME(IT) TIME(TOT) DIAG + 1 -54.35871954 -54.35871954 0.00D+00 0.59D+00 0 0 0.00 0.02 start + 2 -54.38773225 -0.02901271 0.37D-01 0.11D+00 1 0 0.00 0.02 diag2 + 3 -54.38832005 -0.00058780 0.84D-02 0.27D-01 2 0 0.00 0.02 diag2 + 4 -54.38841370 -0.00009365 0.25D-02 0.13D-01 3 0 0.00 0.02 diag2 + 5 -54.38841424 -0.00000053 0.18D-03 0.99D-03 4 0 0.00 0.02 diag2 + 6 -54.38841424 -0.00000000 0.42D-06 0.15D-05 5 0 0.01 0.03 diag2 + 7 -54.38841424 0.00000000 0.29D-08 0.11D-07 0 0 0.00 0.03 diag + + Final alpha occupancy: 2 1 1 0 1 0 0 + Final beta occupancy: 2 0 0 0 0 0 0 + + !RHF STATE 1.8 Energy -54.388414236937 + RHF One-electron energy -73.949784753221 + RHF Two-electron energy 19.561370516285 + RHF Kinetic energy 54.388183347818 + RHF Nuclear energy 0.000000000000 + RHF Virial quotient -1.000004245207 + + !RHF STATE 1.8 Dipole moment 0.00000000 0.00000000 0.00000000 + Dipole moment /Debye 0.00000000 0.00000000 0.00000000 + + ELECTRON ORBITALS + ================= + + Orbital Occupation Energy Cen Mu Typ Coefficients + 1.1 2.00000 -15.62769 1 1 s 1.00000 + 2.1 2.00000 -0.94227 1 2 s 1.00000 + 1.2 1.00000 -0.56237 1 1 px 1.00000 + 1.3 1.00000 -0.56237 1 1 py 1.00000 + 1.5 1.00000 -0.56237 1 1 pz 1.00000 + + + HOMO 1.5 -0.562370 = -15.3029eV + LUMO 2.2 0.880431 = 23.9578eV + LUMO-HOMO 1.442802 = 39.2606eV + + Orbitals saved in record 2100.2 + + + ********************************************************************************************************************************** + DATASETS * FILE NREC LENGTH (MB) RECORD NAMES + 1 18 28.55 500 610 700 900 950 970 1000 129 960 1100 + VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S + 1400 1410 1200 1210 1080 1600 1650 1700 + T V H0 H01 AOSYM SMH MOLCAS OPER + + 2 4 0.35 700 1000 520 2100 + GEOM BASIS MCVARS RHF + + PROGRAMS * TOTAL HF-SCF INT + CPU TIMES * 1.63 0.74 0.39 + REAL TIME * 7.19 SEC + DISK USED * 28.94 MB (local), 527.14 MB (total) + GA USED * 0.00 MB (max) 0.00 MB (current) + ********************************************************************************************************************************** + + + PROGRAM * CCSD (Unrestricted open-shell coupled cluster) Authors: C. Hampel, H.-J. Werner, 1991, M. Deegan, P.J. Knowles, 1992 + + + Convergence thresholds: THRVAR = 1.00D-08 THRDEN = 1.00D-06 + + Number of core orbitals: 1 ( 1 0 0 0 0 0 0 0 ) + Number of closed-shell orbitals: 1 ( 1 0 0 0 0 0 0 0 ) + Number of active orbitals: 3 ( 0 1 1 0 1 0 0 0 ) + Number of external orbitals: 9 ( 3 1 1 1 1 1 1 0 ) + + Number of N-1 electron functions: 5 + Number of N-2 electron functions: 10 + Number of singly external CSFs: 12 + Number of doubly external CSFs: 138 + Total number of CSFs: 150 + + Molecular orbitals read from record 2100.2 Type=RHF/CANONICAL + + Integral transformation finished. Total CPU: 0.04 sec, npass= 1 Memory used: 0.07 MW + + Starting RMP2 calculation, locsing= 0 + + ITER. SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) DIIS TIME + 1 1.02039334 -0.07278335 -54.46119759 -0.07278335 -0.00020471 0.38D-05 0.52D-04 1 1 0.10 + 2 1.02053061 -0.07300412 -54.46141836 -0.00022076 -0.00000014 0.10D-09 0.34D-07 2 2 0.12 + 3 1.02053183 -0.07300573 -54.46141997 -0.00000161 -0.00000000 0.18D-11 0.95D-11 3 3 0.12 + 4 1.02053182 -0.07300572 -54.46141996 0.00000001 -0.00000000 0.67D-15 0.25D-14 4 4 0.12 + + Norm of t1 vector: 0.02959147 S-energy: -0.00172365 T1 diagnostic: 0.00068731 + Norm of t2 vector: 0.14020043 P-energy: -0.07128207 + Alpha-Beta: -0.04979092 + Alpha-Alpha: -0.02149115 + Beta-Beta: 0.00000000 + + Spin contamination 0.00013927 + Reference energy -54.388414236937 + RHF-RMP2 correlation energy -0.073005721083 + !RHF-RMP2 energy -54.461419958020 + + Starting UCCSD calculation + + ITER. SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) DIIS TIME + 1 1.02800792 -0.08499385 -54.47340809 -0.08499385 -0.00353707 0.44D-04 0.94D-03 1 1 0.16 + 2 1.03107787 -0.08914846 -54.47756270 -0.00415461 -0.00004118 0.24D-06 0.11D-04 2 2 0.20 + 3 1.03127367 -0.08932326 -54.47773749 -0.00017479 -0.00000065 0.11D-06 0.14D-06 3 3 0.22 + 4 1.03128825 -0.08933977 -54.47775400 -0.00001651 -0.00000002 0.91D-09 0.47D-08 4 4 0.24 + 5 1.03128271 -0.08933243 -54.47774667 0.00000733 -0.00000000 0.67D-10 0.16D-09 5 5 0.26 + 6 1.03128507 -0.08933541 -54.47774965 -0.00000298 -0.00000000 0.64D-11 0.28D-11 6 6 0.27 + 7 1.03128438 -0.08933448 -54.47774872 0.00000093 -0.00000000 0.14D-12 0.10D-12 6 1 0.29 + + Norm of t1 vector: 0.03509621 S-energy: -0.00204908 T1 diagnostic: 0.00030073 + D1 diagnostic: 0.00063963 + D2 diagnostic: 0.15004576 (internal) + Norm of t2 vector: 0.17335696 P-energy: -0.08728541 + Alpha-Beta: -0.06323921 + Alpha-Alpha: -0.02404620 + Beta-Beta: 0.00000000 + + Spin contamination 0.00001507 + + + RESULTS + ======= + + Reference energy -54.388414236937 + UCCSD singles energy -0.002049075709 + UCCSD pair energy -0.087285409135 + UCCSD correlation energy -0.089334484844 + + !RHF-UCCSD energy -54.477748721781 + + Program statistics: + + Available memory in ccsd: 366234205 + Min. memory needed in ccsd: 1745 + Max. memory used in ccsd: 1831 + Max. memory used in cckext: 34467 ( 7 integral passes) + Max. memory used in cckint: 66459 ( 1 integral passes) + + + + ********************************************************************************************************************************** + DATASETS * FILE NREC LENGTH (MB) RECORD NAMES + 1 18 28.55 500 610 700 900 950 970 1000 129 960 1100 + VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S + 1400 1410 1200 1210 1080 1600 1650 1700 + T V H0 H01 AOSYM SMH MOLCAS OPER + + 2 4 0.35 700 1000 520 2100 + GEOM BASIS MCVARS RHF + + PROGRAMS * TOTAL UCCSD HF-SCF INT + CPU TIMES * 2.15 0.47 0.74 0.39 + REAL TIME * 7.88 SEC + DISK USED * 28.95 MB (local), 527.36 MB (total) + SF USED * 0.04 MB + GA USED * 0.00 MB (max) 0.00 MB (current) + ********************************************************************************************************************************** + + UCCSD/cc-pVDZ energy= -54.477748721781 + + UCCSD HF-SCF + -54.47774872 -54.38841424 + ********************************************************************************************************************************** + Molpro calculation terminated diff --git a/arc/testing/sp/ONHO(T)_sp_CCSD(T).out b/arc/testing/sp/ONHO(T)_sp_CCSD(T).out new file mode 100644 index 0000000000..ca9171bda7 --- /dev/null +++ b/arc/testing/sp/ONHO(T)_sp_CCSD(T).out @@ -0,0 +1,546 @@ + + Working directory : /tmp/molpro.itm5kNVNkD/ + Global scratch directory : /tmp/molpro.itm5kNVNkD/ + Wavefunction directory : /srv01/technion/alongd/wfu/ + Main file repository : /tmp/molpro.itm5kNVNkD/ + + id : dana + + Nodes nprocs + tech-wn215 9 + Distribution of processes: nprocs(total)= 10 nprocs(compute)= 9 nprocs(helper)= 1 + GA implementation: MPI file + GA implementation (serial work in mppx): MPI file + + Using customized tuning parameters: mindgm=1; mindgv=20; mindgc=4; mindgr=1; noblas=0; minvec=7 + default implementation of scratch files=sf + + + Variables initialized (1009), CPU time= 0.01 sec + ***,ONHO[T] + memory,81,m; + + geometry={angstrom; + O 1.16311000 -0.40014300 -0.07491100 + N -0.01347400 0.09324800 0.23645300 + O -0.98340400 -0.73991000 -0.06323900 + H -0.16623100 1.04680500 -0.09830300} + + basis=cc-pvtz-f12 + + + + int; + {hf; + maxit,1000; + wf,spin=2,charge=0;} + + uccsd(t)-f12; + + + + Commands initialized (810), CPU time= 0.01 sec, 661 directives. + Default parameters read. Elapsed time= 0.19 sec + + Checking input... + Passed +1 + + + *** PROGRAM SYSTEM MOLPRO *** + Copyright, TTI GmbH Stuttgart, 2015 + Version 2021.2 linked Jul 16 2021 12:17:16 + + + ********************************************************************************************************************************** + LABEL * ONHO[T] + 64 bit mpp version DATE: 22-May-23 TIME: 05:03:35 + ********************************************************************************************************************************** + + SHA1: dade016a989826d9d859d6207854b99675d53db3 + ********************************************************************************************************************************** + + Memory per process: 81 MW + Total memory per node: 729 MW + + GA preallocation disabled + GA check disabled + + Variable memory set to 81.0 MW + + + Geometry recognized as XYZ + + SETTING BASIS = CC-PVTZ-F12 + + + Using spherical harmonics + + Library entry O S cc-pVTZ-F12 selected for orbital group 1 + Library entry O P cc-pVTZ-F12 selected for orbital group 1 + Library entry O D cc-pVTZ-F12 selected for orbital group 1 + Library entry O F cc-pVTZ-F12 selected for orbital group 1 + Library entry N S cc-pVTZ-F12 selected for orbital group 2 + Library entry N P cc-pVTZ-F12 selected for orbital group 2 + Library entry N D cc-pVTZ-F12 selected for orbital group 2 + Library entry N F cc-pVTZ-F12 selected for orbital group 2 + Library entry H S cc-pVTZ-F12 selected for orbital group 4 + Library entry H P cc-pVTZ-F12 selected for orbital group 4 + Library entry H D cc-pVTZ-F12 selected for orbital group 4 + + + PROGRAM * SEWARD (Integral evaluation for generally contracted gaussian basis sets) Author: Roland Lindh, 1990 + + Geometry written to block 1 of record 700 + + + Point group C1 + + + + ATOMIC COORDINATES + + NR ATOM CHARGE X Y Z + + 1 O 8.00 2.197959353 -0.756160681 -0.141561274 + 2 N 7.00 -0.025462170 0.176213182 0.446831411 + 3 O 8.00 -1.858364230 -1.398227257 -0.119504390 + 4 H 1.00 -0.314131063 1.978174756 -0.185765747 + + Bond lengths in Bohr (Angstrom) + + 1-2 2.481759505 2-3 2.481759234 2-4 1.931469495 + ( 1.313290573) ( 1.313290430) ( 1.022089640) + + Bond angles + + 1-2-3 111.66797230 1-2-4 114.00065603 3-2-4 114.00063237 + + NUCLEAR CHARGE: 24 + NUMBER OF PRIMITIVE AOS: 237 + NUMBER OF SYMMETRY AOS: 209 + NUMBER OF CONTRACTIONS: 177 ( 177A ) + NUMBER OF INNER CORE ORBITALS: 0 ( 0A ) + NUMBER OF OUTER CORE ORBITALS: 3 ( 3A ) + NUMBER OF VALENCE ORBITALS: 13 ( 13A ) + + + NUCLEAR REPULSION ENERGY 68.64579960 + + + Eigenvalues of metric + + 1 0.187E-03 0.375E-03 0.383E-03 0.529E-03 0.542E-03 0.557E-03 0.593E-03 0.650E-03 + + + Contracted 2-electron integrals neglected if value below 1.0D-11 + AO integral compression algorithm 1 Integral accuracy 1.0D-11 + + 614.728 MB (compressed) written to integral file ( 50.3%) + + Node minimum: 55.050 MB, node maximum: 78.119 MB + + + NUMBER OF SORTED TWO-ELECTRON INTEGRALS: 13789125. BUFFER LENGTH: 32768 + NUMBER OF SEGMENTS: 1 SEGMENT LENGTH: 13789125 RECORD LENGTH: 524288 + + Memory used in sort: 14.35 MW + + SORT1 READ 152879757. AND WROTE 13315607. INTEGRALS IN 39 RECORDS. CPU TIME: 3.29 SEC, REAL TIME: 3.52 SEC + SORT2 READ 119810212. AND WROTE 124086381. INTEGRALS IN 2277 RECORDS. CPU TIME: 0.34 SEC, REAL TIME: 1.05 SEC + + Node minimum: 13780375. Node maximum: 13794378. integrals + + OPERATOR DM FOR CENTER 0 COORDINATES: 0.000000 0.000000 0.000000 + + + ********************************************************************************************************************************** + DATASETS * FILE NREC LENGTH (MB) RECORD NAMES + 1 18 29.74 500 610 700 900 950 970 1000 129 960 1100 + VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S + 1400 1410 1200 1210 1080 1600 1650 1700 + T V H0 H01 AOSYM SMH MOLCAS OPER + + PROGRAMS * TOTAL INT + CPU TIMES * 5.00 4.74 + REAL TIME * 6.76 SEC + DISK USED * 30.09 MB (local), 2.18 GB (total) + GA USED * 0.00 MB (max) 0.00 MB (current) + ********************************************************************************************************************************** + + + Program * Restricted Hartree-Fock + + Orbital guess generated from atomic densities. Full valence occupancy: 16 + + Initial alpha occupancy: 13 + Initial beta occupancy: 11 + + NELEC= 24 SYM=1 MS2= 2 THRE=1.0D-08 THRD=3.2D-06 THRG=3.2D-06 HFMA2=F DIIS_START=2 DIIS_MAX=10 DIIS_INCORE=F + + Level shifts: 0.00 (CLOSED) 0.00 (OPEN) 0.30 (GAP_MIN) + + ITER ETOT DE GRAD DDIFF DIIS NEXP TIME(IT) TIME(TOT) DIAG + 1 -204.50816248 -204.50816248 0.00D+00 0.51D-01 0 0 0.20 0.37 start + 2 -204.56862228 -0.06045980 0.69D-02 0.73D-02 1 0 0.19 0.56 diag2 + 3 -204.60593664 -0.03731435 0.47D-02 0.34D-02 2 0 0.19 0.75 diag2 + 4 -204.61271823 -0.00678159 0.76D-03 0.84D-03 3 0 0.21 0.96 diag2 + 5 -204.61956180 -0.00684358 0.52D-03 0.73D-03 4 0 0.20 1.16 diag2 + 6 -204.62468678 -0.00512498 0.51D-03 0.53D-03 5 0 0.18 1.34 diag2 + 7 -204.63097347 -0.00628669 0.52D-03 0.67D-03 6 0 0.18 1.52 diag2 + 8 -204.61701361 0.01395986 0.53D-03 0.16D-02 7 0 0.19 1.71 diag2 + 9 -204.59732447 0.01968915 0.48D-03 0.26D-02 8 0 0.19 1.90 diag2 + 10 -204.59669942 0.00062504 0.69D-03 0.36D-03 9 0 0.19 2.09 diag2/orth + 11 -204.59156820 0.00513122 0.90D-03 0.17D-02 9 0 0.18 2.27 diag2 + 12 -204.58675148 0.00481673 0.75D-03 0.89D-03 9 0 0.20 2.47 diag2 + 13 -204.59097883 -0.00422735 0.12D-02 0.57D-03 9 0 0.19 2.66 diag2 + 14 -204.59032950 0.00064933 0.72D-03 0.16D-03 9 0 0.20 2.86 diag2 + 15 -204.58784321 0.00248630 0.81D-03 0.32D-03 9 0 0.20 3.06 diag2 + 16 -204.59212620 -0.00428299 0.11D-02 0.65D-03 9 0 0.19 3.25 diag2 + 17 -204.59381255 -0.00168635 0.61D-03 0.46D-03 9 0 0.20 3.45 diag2 + 18 -204.59427810 -0.00046555 0.29D-03 0.28D-03 9 0 0.20 3.65 diag2 + 19 -204.59430073 -0.00002262 0.12D-03 0.22D-03 9 0 0.19 3.84 diag2 + 20 -204.59428590 0.00001482 0.37D-04 0.11D-03 9 0 0.19 4.03 diag2/orth + 21 -204.59430477 -0.00001887 0.53D-04 0.92D-04 9 0 0.20 4.23 diag2 + 22 -204.59430467 0.00000010 0.54D-05 0.17D-04 9 0 0.19 4.42 diag2 + 23 -204.59430508 -0.00000040 0.65D-05 0.12D-04 9 0 0.20 4.62 diag2 + 24 -204.59430509 -0.00000001 0.88D-06 0.31D-05 9 0 0.20 4.82 diag2 + 25 -204.59430509 -0.00000001 0.84D-06 0.94D-06 0 0 0.18 5.00 diag + + Final alpha occupancy: 13 + Final beta occupancy: 11 + + !RHF STATE 1.1 Energy -204.594305094369 + RHF One-electron energy -416.979880956712 + RHF Two-electron energy 143.739776264723 + RHF Kinetic energy 204.276244177975 + RHF Nuclear energy 68.645799597620 + RHF Virial quotient -1.001557013728 + + !RHF STATE 1.1 Dipole moment -0.19669853 1.24700707 0.06345251 + Dipole moment /Debye -0.49995780 3.16957581 0.16128018 + + Orbital energies: + + 1.1 2.1 3.1 4.1 5.1 6.1 7.1 8.1 9.1 10.1 + -20.654690 -20.654619 -15.797142 -1.550131 -1.350629 -1.028033 -0.767777 -0.712159 -0.689357 -0.528380 + + 11.1 12.1 13.1 14.1 15.1 + -0.490295 -0.568787 -0.485154 0.051998 0.085680 + + + HOMO 13.1 -0.485154 = -13.2017eV + LUMO 14.1 0.051998 = 1.4149eV + LUMO-HOMO 0.537152 = 14.6166eV + + Orbitals saved in record 2100.2 + + + ********************************************************************************************************************************** + DATASETS * FILE NREC LENGTH (MB) RECORD NAMES + 1 18 29.74 500 610 700 900 950 970 1000 129 960 1100 + VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S + 1400 1410 1200 1210 1080 1600 1650 1700 + T V H0 H01 AOSYM SMH MOLCAS OPER + + 2 4 3.66 700 1000 520 2100 + GEOM BASIS MCVARS RHF + + PROGRAMS * TOTAL HF-SCF INT + CPU TIMES * 10.08 5.06 4.74 + REAL TIME * 12.33 SEC + DISK USED * 37.79 MB (local), 2.25 GB (total) + GA USED * 0.00 MB (max) 0.00 MB (current) + ********************************************************************************************************************************** + + + PROGRAM * CCSD (Unrestricted open-shell coupled cluster) Authors: C. Hampel, H.-J. Werner, 1991, M. Deegan, P.J. Knowles, 1992 + + UCCSD-F12 implementation by G. Knizia and H.-J. Werner, 2008 + + Density fitting integral evaluation by F.R. Manby, 2003,2007, G. Knizia, 2010 + + + Basis set VTZ-F12/JKFIT generated. Number of basis functions: 358 + Basis set CC-PVTZ-F12/OPTRI generated. Number of basis functions: 266 + Basis set CC-PVTZ-F12/MP2FIT generated. Number of basis functions: 364 + + Convergence thresholds: THRVAR = 1.00D-08 THRDEN = 1.00D-06 + + CCSD(T) terms to be evaluated (factor= 1.000) + + + Number of core orbitals: 3 ( 3 ) + Number of closed-shell orbitals: 8 ( 8 ) + Number of active orbitals: 2 ( 2 ) + Number of external orbitals: 164 ( 164 ) + + For full I/O caching in triples, increase memory by 4.40 Mwords to 85.45 Mwords. + + Number of N-1 electron functions: 18 + Number of N-2 electron functions: 153 + Number of singly external CSFs: 2988 + Number of doubly external CSFs: 3204215 + Total number of CSFs: 3207203 + + Molecular orbitals read from record 2100.2 Type=RHF/CANONICAL + + Integral transformation finished. Total CPU: 3.77 sec, npass= 1 Memory used: 34.24 MW + + Geminal basis: OPTFULL GEM_TYPE=SLATER BETA=1.0 NGEM=6 + + Optimizing Gaussian exponents for each gem_beta + + Geminal optimization for beta= 1.0000 + Weight function: m=0, omega= 1.4646 + + Augmented Hessian optimization of geminal fit. Trust ratio= 0.40000 + Convergence reached after 2 iterations. Final gradient= 8.66D-16, Step= 4.23D-06, Delta= 1.28D-09 + + Alpha: 0.19532 0.81920 2.85917 9.50073 35.69989 197.79328 + Coeff: 0.27070 0.30552 0.18297 0.10986 0.06810 0.04224 + + + WFN_F12=FIX,EG DECOUPLE_EXPL=F HYBRID=0 NOX=F SEMIINT_F12=T CORE_SINGLES=F + + + AO(A)-basis ORBITAL loaded. Number of functions: 177 + RI(R)-basis CC-PVTZ-F12/OPTRI loaded. Number of functions: 266 + DF-basis VTZ-F12/JKFIT loaded. Number of functions: 358 + + Screening thresholds: THRAO= 1.00D-10 THRMO= 1.00D-09 THRPROD= 1.00D-09 + THRSW= 1.00D-05 THROV= 1.00D-12 THRAOF12= 1.00D-08 + + CPU time for one-electron matrices 0.43 sec + + Construction of ABS: + Pseudo-inverse stability 1.22E-12 + Smallest eigenvalue of S 5.64E-04 (threshold= 1.00E-08) + Ratio eigmin/eigmax 8.61E-05 (threshold= 1.00E-09) + Smallest eigenvalue of S kept 5.64E-04 (threshold= 5.64E-04, 0 functions deleted, 266 kept) + + Construction of CABS: + Pseudo-inverse stability 1.09E-10 + Smallest eigenvalue of S 1.32E-06 (threshold= 1.00E-08) + Ratio eigmin/eigmax 1.32E-06 (threshold= 1.00E-09) + Smallest eigenvalue of S kept 1.32E-06 (threshold= 1.32E-06, 0 functions deleted, 266 kept) + + CPU time for basis constructions 0.04 sec + Fock operators(MO) rebuilt from dump record. + CPU time for Fock operator transformation 0.07 sec + + TOTAL ALPHA BETA + Singles Contributions MO -0.014322449 -0.006918469 -0.007403980 + Singles Contributions CABS -0.001920198 -0.001097200 -0.000822997 + Pure DF-RHF relaxation -0.001885518 + + CPU time for RHF CABS relaxation 0.07 sec + CPU time for singles (tot) 0.16 sec + + AO(A)-basis ORBITAL loaded. Number of functions: 177 + RI(R)-basis CC-PVTZ-F12/OPTRI loaded. Number of functions: 266 + DF-basis CC-PVTZ-F12/MP2FIT loaded. Number of functions: 364 + + Screening thresholds: THRAO= 1.00D-10 THRMO= 1.00D-09 THRPROD= 1.00D-09 + THRSW= 1.00D-05 THROV= 1.00D-12 THRAOF12= 1.00D-08 + + CPU time for transformed integrals 1.80 sec + CPU time for F12 matrices 1.76 sec + + Diagonal F12 ansatz with fixed amplitudes: TS= 0.5000 TT= 0.2500 TN= 0.3750 + + ITER. SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE VAR CPU MICRO DIIS + 1 1.21786532 -0.79736109 -205.39355170 -7.9925E-01 2.07E-01 0.11 1 1 1 0 0 + 2 1.21492015 -0.79229656 -205.38848718 5.0645E-03 4.26E-04 0.42 0 0 0 1 1 + 3 1.21608606 -0.79324301 -205.38943362 -9.4644E-04 7.61E-06 0.81 0 0 0 2 2 + 4 1.21613146 -0.79325368 -205.38944429 -1.0674E-05 6.90E-08 1.31 0 0 0 3 3 + 5 1.21613965 -0.79325379 -205.38944441 -1.1263E-07 4.78E-10 1.95 0 0 0 4 4 + + - - Continuing with F12/conv. amplitude coupling turned on. + + 6 1.21613596 -0.79359212 -205.38978273 -3.3844E-04 6.02E-05 2.39 1 1 1 1 1 + 7 1.21613414 -0.79359206 -205.38978268 5.3836E-08 4.00E-09 2.97 1 1 1 2 2 + + CPU time for iterative RMP2-F12 2.97 sec + + + DF-RMP2-F12 doubles corrections: + - - - - - - - - - - - - - - - - + Approx. TOTAL A-B A-A B-B + RMP2-F12/3C(FIX) -0.059649753 -0.054741330 -0.003089795 -0.001818628 + RMP2-F12/3*C(FIX) -0.059311483 -0.054626021 -0.002960263 -0.001725199 + RMP2-F12/3*C(DX) -0.059629319 -0.054908743 -0.002983489 -0.001737086 + RMP2-F12/3*C(FIX,DX) -0.063951701 -0.058838159 -0.003237216 -0.001876326 + + DF-RMP2-F12 doubles energies: + - - - - - - - - - - - - - - - + Approx. TOTAL A-B A-A B-B + RMP2 -0.719619861 -0.521365148 -0.094171054 -0.104083659 + RMP2-F12/3C(FIX) -0.779269614 -0.576106478 -0.097260848 -0.105902288 + RMP2-F12/3*C(FIX) -0.778931344 -0.575991168 -0.097131317 -0.105808859 + RMP2-F12/3*C(DX) -0.779249179 -0.576273891 -0.097154543 -0.105820746 + RMP2-F12/3*C(FIX,DX) -0.783571562 -0.580203307 -0.097408270 -0.105959985 + + + Reference energy -204.594305094369 + CABS relaxation correction to RHF -0.001885518432 + New reference energy -204.596190612801 + + RMP2-F12 singles (MO) energy -0.014322449179 + RMP2-F12 pair energy -0.779269613905 + RMP2-F12 correlation energy -0.793592063084 + + !RMP2-F12/3C(FIX) energy -205.389782675885 + + Starting RMP2 calculation, locsing= 0 + + ITER. SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) DIIS TIME + 1 1.21201001 -0.73069539 -205.32500049 -0.73069539 -0.00283164 0.89D-04 0.13D-02 1 1 12.08 + 2 1.21578131 -0.73384920 -205.32815429 -0.00315380 -0.00002504 0.86D-06 0.15D-04 2 2 12.61 + 3 1.21613420 -0.73399532 -205.32830042 -0.00014613 -0.00000027 0.79D-08 0.14D-06 3 3 13.06 + 4 1.21614044 -0.73399281 -205.32829791 0.00000251 -0.00000000 0.14D-09 0.14D-08 4 4 13.41 + 5 1.21614016 -0.73399262 -205.32829772 0.00000019 -0.00000000 0.66D-11 0.15D-10 5 5 13.93 + + Norm of t1 vector: 0.10183213 S-energy: -0.01432245 T1 diagnostic: 0.00131542 + Norm of t2 vector: 0.45361920 P-energy: -0.71967017 + Alpha-Beta: -0.52156532 + Alpha-Alpha: -0.09407779 + Beta-Beta: -0.10402706 + + Spin contamination 0.00137406 + Reference energy -204.594305094369 + CABS singles correction -0.001885518432 + New reference energy -204.596190612801 + RHF-RMP2 correlation energy -0.733992624992 + !RHF-RMP2 energy -205.330183237793 + + F12/3C(FIX) correction -0.059649753206 + RHF-RMP2-F12 correlation energy -0.793642378199 + !RHF-RMP2-F12 total energy -205.389832991000 + + Starting UCCSD calculation + + ITER. SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) DIIS TIME + 1 1.17899064 -0.67643819 -205.27074328 -0.67643819 -0.03119289 0.94D-02 0.50D-02 1 1 18.74 + 2 1.20180801 -0.70103039 -205.29533548 -0.02459220 -0.00352011 0.92D-03 0.10D-02 2 2 23.16 + 3 1.21499994 -0.70363982 -205.29794491 -0.00260943 -0.00093563 0.73D-03 0.13D-03 3 3 28.22 + 4 1.22987595 -0.70713176 -205.30143686 -0.00349194 -0.00029171 0.21D-03 0.48D-04 4 4 33.44 + 5 1.24217753 -0.70869506 -205.30300015 -0.00156330 -0.00009832 0.94D-04 0.13D-04 5 5 37.99 + 6 1.24926455 -0.70918738 -205.30349248 -0.00049233 -0.00005217 0.61D-04 0.52D-05 6 6 42.51 + 7 1.25300578 -0.70938820 -205.30369330 -0.00020082 -0.00004633 0.60D-04 0.33D-05 6 1 47.41 + 8 1.25429767 -0.70943555 -205.30374065 -0.00004735 -0.00004603 0.60D-04 0.31D-05 6 3 52.77 + 9 1.25415395 -0.70945031 -205.30375541 -0.00001476 -0.00004589 0.60D-04 0.31D-05 6 2 57.43 + 10 1.25152101 -0.70927518 -205.30358027 0.00017514 -0.00004530 0.59D-04 0.31D-05 6 4 61.87 + 11 1.24627889 -0.70865498 -205.30296008 0.00062019 -0.00003825 0.47D-04 0.31D-05 6 5 66.52 + 12 1.26089888 -0.70813118 -205.30243627 0.00052380 -0.00003093 0.37D-04 0.28D-05 6 6 71.70 + 13 1.28815306 -0.70769691 -205.30200201 0.00043427 -0.00002188 0.24D-04 0.26D-05 6 1 76.51 + 14 1.44079753 -0.70672817 -205.30103326 0.00096874 -0.00000696 0.65D-05 0.11D-05 6 3 81.43 + 15 1.43362614 -0.70660919 -205.30091429 0.00011897 -0.00000575 0.41D-05 0.15D-05 6 6 85.97 + 16 1.45642320 -0.70636456 -205.30066965 0.00024464 -0.00000210 0.10D-05 0.79D-06 6 1 90.39 + 17 1.47495896 -0.70626229 -205.30056739 0.00010226 -0.00000051 0.24D-06 0.20D-06 6 3 95.59 + 18 1.47924993 -0.70621370 -205.30051879 0.00004860 -0.00000019 0.13D-06 0.46D-07 6 5 99.90 + 19 1.48410957 -0.70618830 -205.30049340 0.00002540 -0.00000008 0.69D-07 0.16D-07 6 3 104.62 + 20 1.47752988 -0.70619886 -205.30050395 -0.00001055 -0.00000003 0.20D-07 0.57D-08 6 6 108.81 + 21 1.47910940 -0.70619396 -205.30049906 0.00000489 -0.00000002 0.11D-07 0.42D-08 6 1 114.00 + 22 1.48251864 -0.70617939 -205.30048448 0.00001458 -0.00000001 0.35D-08 0.20D-08 6 5 119.75 + 23 1.48011544 -0.70618691 -205.30049201 -0.00000753 -0.00000000 0.94D-09 0.50D-09 6 6 125.75 + 24 1.48129711 -0.70618087 -205.30048597 0.00000604 -0.00000000 0.11D-09 0.85D-10 6 2 130.53 + 25 1.48143355 -0.70618021 -205.30048531 0.00000066 -0.00000000 0.43D-10 0.23D-10 6 4 134.97 + + Norm of t1 vector: 0.51307486 S-energy: -0.01327348 T1 diagnostic: 0.08392018 + D1 diagnostic: 0.32815588 + D2 diagnostic: 0.18493718 (internal) + Norm of t2 vector: 0.46710570 P-energy: -0.69290674 + Alpha-Beta: -0.52239075 + Alpha-Alpha: -0.08223939 + Beta-Beta: -0.08827659 + + Singles amplitudes (print threshold = 0.500E-01): + + I SYM. A A T(IA) [Beta-Beta] + + 5 1 1 -0.05148975 + 6 1 2 0.17443263 + 7 1 1 -0.46095969 + + Doubles amplitudes (print threshold = 0.500E-01): + + I J SYM. A SYM. B A B T(IJ, AB) [Beta-Beta] + + 7 4 1 1 1 2 0.05340832 + 7 4 1 1 2 1 -0.05340832 + 8 7 1 1 1 2 -0.12716886 + 8 7 1 1 2 1 0.12716886 + + Spin contamination 0.00324895 + + For full I/O caching in triples, increase memory by 11.36 Mwords to 92.41 Mwords. + + + RESULTS + ======= + + Reference energy -204.594305094369 + CABS relaxation correction to RHF -0.001885518432 + New reference energy -204.596190612801 + + F12 corrections for ansatz 3C(FIX) added to UCCSD energy. Coupling mode: 15 + + UCCSD-F12a singles energy -0.013273475828 + UCCSD-F12a pair energy -0.751491924860 + UCCSD-F12a correlation energy -0.764765400688 + Triples (T) contribution -0.039595621856 + Total correlation energy -0.804361022544 + + RHF-UCCSD-F12a energy -205.360956013489 + RHF-UCCSD[T]-F12a energy -205.404541008915 + RHF-UCCSD-T-F12a energy -205.399718174377 + !RHF-UCCSD(T)-F12a energy -205.400551635345 + + F12 corrections for ansatz 3C(FIX) added to UCCSD energy. Coupling mode: 15 + + UCCSD-F12b singles energy -0.013273475828 + UCCSD-F12b pair energy -0.741609941455 + UCCSD-F12b correlation energy -0.754883417282 + Triples (T) contribution -0.039595621856 + Total correlation energy -0.794479039139 + + RHF-UCCSD-F12b energy -205.351074030083 + RHF-UCCSD[T]-F12b energy -205.394659025510 + RHF-UCCSD-T-F12b energy -205.389836190972 + !RHF-UCCSD(T)-F12b energy -205.390669651940 + + Program statistics: + + Available memory in ccsd: 80999087 + Min. memory needed in ccsd: 9591163 + Max. memory used in ccsd: 13497261 + Max. memory used in cckext: 10315093 (26 integral passes) + Max. memory used in cckint: 34238127 ( 1 integral passes) + + + + ********************************************************************************************************************************** + DATASETS * FILE NREC LENGTH (MB) RECORD NAMES + 1 18 29.74 500 610 700 900 950 970 1000 129 960 1100 + VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S + 1400 1410 1200 1210 1080 1600 1650 1700 + T V H0 H01 AOSYM SMH MOLCAS OPER + + 2 5 3.89 700 1000 520 2100 7360 + GEOM BASIS MCVARS RHF F12ABS + + PROGRAMS * TOTAL UCCSD(T) HF-SCF INT + CPU TIMES * 193.70 183.60 5.06 4.74 + REAL TIME * 240.06 SEC + DISK USED * 419.99 MB (local), 5.61 GB (total) + SF USED * 2.86 GB + GA USED * 3.05 MB (max) 0.00 MB (current) + ********************************************************************************************************************************** + + UCCSD(T)-F12/cc-pVTZ-F12 energy= -205.390669651940 + + UCCSD(T)-F12 HF-SCF + -205.39066965 -204.59430509 + ********************************************************************************************************************************** + Molpro calculation terminated diff --git a/arc/testing/sp/TS_x118_sp_CCSD(T).out b/arc/testing/sp/TS_x118_sp_CCSD(T).out new file mode 100644 index 0000000000..2d285a5414 --- /dev/null +++ b/arc/testing/sp/TS_x118_sp_CCSD(T).out @@ -0,0 +1,531 @@ + + Working directory : /state/partition1/user/alongd/molpro/alongd/a62525-24258041/molpro.wkcIOXi9da/ + Global scratch directory : /state/partition1/user/alongd/molpro/alongd/a62525-24258041/molpro.wkcIOXi9da/ + Wavefunction directory : /home/gridsan/alongd/wfu/ + Main file repository : /state/partition1/user/alongd/molpro/alongd/a62525-24258041/molpro.wkcIOXi9da/ + + id : whgreen + + Nodes nprocs + c-16-10-4 8 + GA implementation: MPI file + GA implementation (serial work in mppx): MPI file + + Using customized tuning parameters: mindgm=1; mindgv=20; mindgc=4; mindgr=1; noblas=0; minvec=7 + default implementation of scratch files=sf + + + Variables initialized (1025), CPU time= 0.03 sec + ***,TS0 + memory,235,m; + + geometry={angstrom; + N -0.00000000 -1.36720300 0.15499300 + O -0.00000000 -1.10333100 -0.98685800 + H -0.00000000 -0.28110100 0.76732400 + O 0.00000000 0.97476200 0.91364300 + O 0.00000000 1.44007500 -0.27062400} + + basis=cc-pvtz-f12 + + + + int; + {hf; + maxit,1000; + wf,spin=2,charge=0;} + + uccsd(t)-f12; + + + + Commands initialized (840), CPU time= 0.02 sec, 684 directives. + Default parameters read. Elapsed time= 2.26 sec + + Checking input... + Passed +1 + + + *** PROGRAM SYSTEM MOLPRO *** + Copyright, TTI GmbH Stuttgart, 2015 + Version 2022.3 linked Wed Nov 30 06:40:34 2022 + + + ********************************************************************************************************************************** + LABEL * TS0 + 64 bit mpp version DATE: 12-Nov-23 TIME: 02:11:19 + ********************************************************************************************************************************** + + SHA1: e31ec9a5ea85254ab76f59d122cbdd51c71cf98b + ********************************************************************************************************************************** + + Memory per process: 235 MW + Total memory per node: 1880 MW + + GA preallocation disabled + GA check disabled + + Variable memory set to 235.0 MW + + + Geometry recognized as XYZ + + SETTING BASIS = CC-PVTZ-F12 + + + Using spherical harmonics + + Library entry N S cc-pVTZ-F12 selected for orbital group 1 + Library entry N P cc-pVTZ-F12 selected for orbital group 1 + Library entry N D cc-pVTZ-F12 selected for orbital group 1 + Library entry N F cc-pVTZ-F12 selected for orbital group 1 + Library entry O S cc-pVTZ-F12 selected for orbital group 2 + Library entry O P cc-pVTZ-F12 selected for orbital group 2 + Library entry O D cc-pVTZ-F12 selected for orbital group 2 + Library entry O F cc-pVTZ-F12 selected for orbital group 2 + Library entry H S cc-pVTZ-F12 selected for orbital group 3 + Library entry H P cc-pVTZ-F12 selected for orbital group 3 + Library entry H D cc-pVTZ-F12 selected for orbital group 3 + + + PROGRAM * SEWARD (Integral evaluation for generally contracted gaussian basis sets) Author: Roland Lindh, 1990 + + Geometry written to block 1 of record 700 + + + Point group Cs + + + + ATOMIC COORDINATES + + NR ATOM CHARGE X Y Z + + 1 N 7.00 0.000000000 -2.583639227 0.292894321 + 2 O 8.00 0.000000000 -2.084993415 -1.864891344 + 3 H 1.00 0.000000000 -0.531203903 1.450032209 + 4 O 8.00 0.000000000 1.842033217 1.726535046 + 5 O 8.00 0.000000000 2.721347349 -0.511405243 + + Bond lengths in Bohr (Angstrom) + + 1-2 2.214652709 1-3 2.356153401 3-4 2.389290323 4-5 2.404489567 + ( 1.171943744) ( 1.246822685) ( 1.264357989) ( 1.272401083) + + Bond angles + + 1-3-4 157.23172603 2-1-3 106.40162738 3-4-5 104.80497390 + + NUCLEAR CHARGE: 32 + NUMBER OF PRIMITIVE AOS: 309 + NUMBER OF SYMMETRY AOS: 272 + NUMBER OF CONTRACTIONS: 230 ( 153A' + 77A" ) + NUMBER OF INNER CORE ORBITALS: 0 ( 0A' + 0A" ) + NUMBER OF OUTER CORE ORBITALS: 4 ( 4A' + 0A" ) + NUMBER OF VALENCE ORBITALS: 17 ( 13A' + 4A" ) + + + NUCLEAR REPULSION ENERGY 109.83171436 + + + Eigenvalues of metric + + 1 0.197E-03 0.289E-03 0.375E-03 0.474E-03 0.513E-03 0.543E-03 0.554E-03 0.594E-03 + 2 0.574E-03 0.688E-03 0.689E-03 0.713E-03 0.526E-02 0.906E-02 0.153E-01 0.236E-01 + + + Contracted 2-electron integrals neglected if value below 1.0D-11 + AO integral compression algorithm 1 Integral accuracy 1.0D-11 + + 768.082 MB (compressed) written to integral file ( 44.9%) + + Node minimum: 86.508 MB, node maximum: 103.023 MB + + + NUMBER OF SORTED TWO-ELECTRON INTEGRALS: 22490649. BUFFER LENGTH: 32768 + NUMBER OF SEGMENTS: 2 SEGMENT LENGTH: 15987537 RECORD LENGTH: 524288 + + Memory used in sort: 16.54 MW + + SORT1 READ 213466560. AND WROTE 20405193. INTEGRALS IN 59 RECORDS. CPU TIME: 3.46 SEC, REAL TIME: 3.86 SEC + SORT2 READ 163669911. AND WROTE 180047406. INTEGRALS IN 3136 RECORDS. CPU TIME: 0.38 SEC, REAL TIME: 0.61 SEC + + Node minimum: 22486955. Node maximum: 22531539. integrals + + OPERATOR DM FOR CENTER 0 COORDINATES: 0.000000 0.000000 0.000000 + + + ********************************************************************************************************************************** + DATASETS * FILE NREC LENGTH (MB) RECORD NAMES + 1 18 29.69 500 610 700 900 950 970 1000 129 960 1100 + VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S + 1400 1410 1200 1210 1080 1600 1650 1700 + T V H0 H01 AOSYM SMH MOLCAS OPER + + PROGRAMS * TOTAL INT + CPU TIMES * 6.04 5.79 + REAL TIME * 15.52 SEC + DISK USED * 30.07 MB (local), 2.74 GB (total) + GA USED * 0.00 MB (max) 0.00 MB (current) + ********************************************************************************************************************************** + + + Program * Restricted Hartree-Fock + + Orbital guess generated from atomic densities. Full valence occupancy: 17 4 + + Initial alpha occupancy: 14 3 + Initial beta occupancy: 13 2 + + NELEC= 32 SYM=2 MS2= 2 THRE=1.0D-08 THRD=3.2D-06 THRG=3.2D-06 HFMA2=F DIIS_START=2 DIIS_MAX=10 DIIS_INCORE=F + + Level shifts: 0.00 (CLOSED) 0.00 (OPEN) 0.30 (GAP_MIN) + + ITER ETOT DE GRAD DDIFF DIIS NEXP TIME(IT) TIME(TOT) DIAG + 1 -279.35505499 -279.35505499 0.00D+00 0.60D-01 0 0 0.24 0.48 start + 2 -279.41410380 -0.05904881 0.68D-02 0.70D-02 1 0 0.29 0.77 diag2 + 3 -279.44563673 -0.03153294 0.45D-02 0.36D-02 2 0 0.32 1.09 diag2 + 4 -279.44998246 -0.00434573 0.13D-02 0.10D-02 3 0 0.26 1.35 diag2 + 5 -279.45240322 -0.00242076 0.45D-03 0.52D-03 4 0 0.23 1.58 diag2 + 6 -279.45451521 -0.00211199 0.30D-03 0.49D-03 5 0 0.22 1.80 diag2 + 7 -279.45731465 -0.00279944 0.26D-03 0.98D-03 6 0 0.19 1.99 diag2 + 8 -279.45766462 -0.00034997 0.14D-03 0.28D-03 7 0 0.19 2.18 fixocc + 9 -279.45776207 -0.00009746 0.89D-04 0.21D-03 8 0 0.28 2.46 diag2 + 10 -279.45776541 -0.00000334 0.31D-04 0.57D-04 9 0 0.30 2.76 diag2/orth + 11 -279.45776989 -0.00000448 0.25D-04 0.52D-04 9 0 0.20 2.96 diag2 + 12 -279.45777042 -0.00000053 0.74D-05 0.18D-04 9 0 0.16 3.12 diag2 + 13 -279.45777070 -0.00000029 0.47D-05 0.11D-04 9 0 0.19 3.31 diag2 + 14 -279.45777082 -0.00000011 0.26D-05 0.64D-05 9 0 0.20 3.51 diag2 + 15 -279.45777090 -0.00000008 0.21D-05 0.74D-05 9 0 0.19 3.70 diag2 + 16 -279.45777092 -0.00000002 0.81D-06 0.43D-05 9 0 0.22 3.92 diag2 + 17 -279.45777092 -0.00000000 0.26D-06 0.85D-06 9 0 0.30 4.22 diag2 + 18 -279.45777092 -0.00000000 0.11D-06 0.14D-06 0 0 0.24 4.46 diag + + Final alpha occupancy: 14 3 + Final beta occupancy: 13 2 + + !RHF STATE 1.2 Energy -279.457770923366 + RHF One-electron energy -602.140346218762 + RHF Two-electron energy 212.850860934237 + RHF Kinetic energy 279.087263922351 + RHF Nuclear energy 109.831714361159 + RHF Virial quotient -1.001327566854 + + !RHF STATE 1.2 Dipole moment 0.00000000 -1.34242416 -0.06399529 + Dipole moment /Debye 0.00000000 -3.41210188 -0.16265981 + + Orbital energies: + + 1.1 2.1 3.1 4.1 5.1 6.1 7.1 8.1 9.1 10.1 + -20.767349 -20.635897 -20.628702 -15.801452 -1.646974 -1.529635 -1.087890 -1.013408 -0.823044 -0.748540 + + 11.1 12.1 13.1 14.1 15.1 16.1 + -0.652471 -0.643207 -0.446403 -0.458011 0.070527 0.077125 + + 1.2 2.2 3.2 4.2 5.2 + -0.703105 -0.601647 -0.521154 0.007333 0.100576 + + + HOMO 14.1 -0.458011 = -12.4631eV + LUMO 4.2 0.007333 = 0.1995eV + LUMO-HOMO 0.465344 = 12.6626eV + + Orbitals saved in record 2100.2 + + + ********************************************************************************************************************************** + DATASETS * FILE NREC LENGTH (MB) RECORD NAMES + 1 18 29.71 500 610 700 900 950 970 1000 129 960 1100 + VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S + 1400 1410 1200 1210 1080 1600 1650 1700 + T V H0 H01 AOSYM SMH MOLCAS OPER + + 2 4 1.35 700 1000 520 2100 + GEOM BASIS MCVARS RHF + + PROGRAMS * TOTAL HF-SCF INT + CPU TIMES * 10.55 4.50 5.79 + REAL TIME * 23.36 SEC + DISK USED * 35.19 MB (local), 2.78 GB (total) + GA USED * 0.00 MB (max) 0.00 MB (current) + ********************************************************************************************************************************** + + + PROGRAM * CCSD (Unrestricted open-shell coupled cluster) Authors: C. Hampel, H.-J. Werner, 1991, M. Deegan, P.J. Knowles, 1992 + + UCCSD-F12 implementation by G. Knizia and H.-J. Werner, 2008 + + Density fitting integral evaluation by F.R. Manby, 2003,2007, G. Knizia, 2010 + + + Basis set VTZ-F12/JKFIT generated. Number of basis functions: 462 + Basis set CC-PVTZ-F12/OPTRI generated. Number of basis functions: 341 + Basis set CC-PVTZ-F12/MP2FIT generated. Number of basis functions: 470 + + Convergence thresholds: THRVAR = 1.00D-08 THRDEN = 1.00D-06 + + CCSD(T) terms to be evaluated (factor= 1.000) + + + Number of core orbitals: 4 ( 4 0 ) + Number of closed-shell orbitals: 11 ( 9 2 ) + Number of active orbitals: 2 ( 1 1 ) + Number of external orbitals: 213 ( 139 74 ) + + Memory could be reduced to 115.32 Mwords without degradation in triples + + Number of N-1 electron functions: 24 + Number of N-2 electron functions: 276 + Number of singly external CSFs: 3035 + Number of doubly external CSFs: 4975525 + Total number of CSFs: 4978560 + + Molecular orbitals read from record 2100.2 Type=RHF/CANONICAL + + Integral transformation finished. Total CPU: 3.29 sec, npass= 1 Memory used: 25.72 MW + + Geminal basis: OPTFULL GEM_TYPE=SLATER BETA=1.0 NGEM=6 + + Optimizing Gaussian exponents for each gem_beta + + Geminal optimization for beta= 1.0000 + Weight function: m=0, omega= 1.4646 + + Augmented Hessian optimization of geminal fit. Trust ratio= 0.40000 + Convergence reached after 2 iterations. Final gradient= 8.73D-16, Step= 4.22D-06, Delta= 1.28D-09 + + Alpha: 0.19532 0.81920 2.85917 9.50073 35.69989 197.79328 + Coeff: 0.27070 0.30552 0.18297 0.10986 0.06810 0.04224 + + + WFN_F12=FIX,EG DECOUPLE_EXPL=F HYBRID=0 NOX=F SEMIINT_F12=T CORE_SINGLES=F + + + AO(A)-basis ORBITAL loaded. Number of functions: 230 + RI(R)-basis CC-PVTZ-F12/OPTRI loaded. Number of functions: 341 + DF-basis VTZ-F12/JKFIT loaded. Number of functions: 462 + + Screening thresholds: THRAO= 1.00D-10 THRMO= 1.00D-09 THRPROD= 1.00D-09 + THRSW= 1.00D-05 THROV= 1.00D-12 THRAOF12= 1.00D-08 + + CPU time for one-electron matrices 0.70 sec + + Construction of ABS: + Pseudo-inverse stability 1.58E-12 + Smallest eigenvalue of S 4.02E-04 (threshold= 1.00E-08) + Ratio eigmin/eigmax 6.18E-05 (threshold= 1.00E-09) + Smallest eigenvalue of S kept 4.02E-04 (threshold= 4.02E-04, 0 functions deleted, 341 kept) + + Construction of CABS: + Pseudo-inverse stability 1.43E-10 + Smallest eigenvalue of S 1.36E-06 (threshold= 1.00E-08) + Ratio eigmin/eigmax 1.36E-06 (threshold= 1.00E-09) + Smallest eigenvalue of S kept 1.36E-06 (threshold= 1.36E-06, 0 functions deleted, 341 kept) + + CPU time for basis constructions 0.04 sec + Fock operators(MO) rebuilt from dump record. + CPU time for Fock operator transformation 0.05 sec + + TOTAL ALPHA BETA + Singles Contributions MO -0.011328795 -0.005595722 -0.005733073 + Singles Contributions CABS -0.002417424 -0.001333226 -0.001084199 + Pure DF-RHF relaxation -0.002379410 + + CPU time for RHF CABS relaxation 0.11 sec + CPU time for singles (tot) 0.22 sec + + AO(A)-basis ORBITAL loaded. Number of functions: 230 + RI(R)-basis CC-PVTZ-F12/OPTRI loaded. Number of functions: 341 + DF-basis CC-PVTZ-F12/MP2FIT loaded. Number of functions: 470 + + Screening thresholds: THRAO= 1.00D-10 THRMO= 1.00D-09 THRPROD= 1.00D-09 + THRSW= 1.00D-05 THROV= 1.00D-12 THRAOF12= 1.00D-08 + + CPU time for transformed integrals 3.72 sec + CPU time for F12 matrices 4.45 sec + + Diagonal F12 ansatz with fixed amplitudes: TS= 0.5000 TT= 0.2500 TN= 0.3750 + + ITER. SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE VAR CPU MICRO DIIS + 1 1.26255534 -1.04279227 -280.50294261 -1.0452E+00 2.56E-01 0.16 1 1 1 0 0 + 2 1.26063161 -1.03904581 -280.49919614 3.7465E-03 3.06E-04 0.46 0 0 0 1 1 + 3 1.26135129 -1.03982313 -280.49997346 -7.7732E-04 2.44E-06 0.83 0 0 0 2 2 + 4 1.26136709 -1.03982773 -280.49997807 -4.6060E-06 1.77E-08 1.37 0 0 0 3 3 + 5 1.26136914 -1.03982777 -280.49997810 -3.2872E-08 1.82E-10 1.99 0 0 0 4 4 + + - - Continuing with F12/conv. amplitude coupling turned on. + + 6 1.26132118 -1.04005442 -280.50020476 -2.2669E-04 7.76E-05 2.41 1 1 1 1 1 + 7 1.26131945 -1.04005474 -280.50020507 -3.1371E-07 4.64E-09 2.95 1 1 1 2 2 + + CPU time for iterative RMP2-F12 2.95 sec + + + DF-RMP2-F12 doubles corrections: + - - - - - - - - - - - - - - - - + Approx. TOTAL A-B A-A B-B + RMP2-F12/3C(FIX) -0.080574720 -0.073961319 -0.003962249 -0.002651151 + RMP2-F12/3*C(FIX) -0.080347751 -0.074004441 -0.003811771 -0.002531539 + RMP2-F12/3*C(DX) -0.080857624 -0.074455168 -0.003848004 -0.002554451 + RMP2-F12/3*C(FIX,DX) -0.087135047 -0.080142792 -0.004206513 -0.002785742 + + DF-RMP2-F12 doubles energies: + - - - - - - - - - - - - - - - + Approx. TOTAL A-B A-A B-B + RMP2 -0.948151220 -0.697483022 -0.124724892 -0.125943306 + RMP2-F12/3C(FIX) -1.028725940 -0.771444341 -0.128687142 -0.128594457 + RMP2-F12/3*C(FIX) -1.028498972 -0.771487463 -0.128536663 -0.128474846 + RMP2-F12/3*C(DX) -1.029008844 -0.771938190 -0.128572896 -0.128497757 + RMP2-F12/3*C(FIX,DX) -1.035286267 -0.777625814 -0.128931405 -0.128729048 + + + Reference energy -279.457770923368 + CABS relaxation correction to RHF -0.002379410418 + New reference energy -279.460150333785 + + RMP2-F12 singles (MO) energy -0.011328794911 + RMP2-F12 pair energy -1.028725940239 + RMP2-F12 correlation energy -1.040054735151 + + !RMP2-F12/3C(FIX) energy -280.500205068936 + + Starting RMP2 calculation, locsing= 0 + + ITER. SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) DIIS TIME + 1 1.25770178 -0.95585278 -280.41362370 -0.95585278 -0.00328179 0.89D-04 0.13D-02 1 1 16.63 + 2 1.26116694 -0.95943355 -280.41720448 -0.00358077 -0.00001455 0.27D-05 0.61D-05 2 2 17.04 + 3 1.26136066 -0.95954036 -280.41731128 -0.00010681 -0.00000016 0.11D-06 0.42D-07 3 3 17.48 + 4 1.26136862 -0.95954198 -280.41731290 -0.00000162 -0.00000000 0.34D-08 0.53D-09 4 4 18.01 + 5 1.26136930 -0.95954210 -280.41731303 -0.00000013 -0.00000000 0.82D-10 0.83D-11 5 5 18.60 + + Norm of t1 vector: 0.08366835 S-energy: -0.01132875 T1 diagnostic: 0.00133293 + Norm of t2 vector: 0.50434998 P-energy: -0.94821335 + Alpha-Beta: -0.69774987 + Alpha-Alpha: -0.12461109 + Beta-Beta: -0.12585240 + + Spin contamination 0.00088354 + Reference energy -279.457770923368 + CABS singles correction -0.002379410418 + New reference energy -279.460150333786 + RHF-RMP2 correlation energy -0.959542104394 + !RHF-RMP2 energy -280.419692438180 + + F12/3C(FIX) correction -0.080574719808 + RHF-RMP2-F12 correlation energy -1.040116824202 + !RHF-RMP2-F12 total energy -280.500267157987 + + Starting UCCSD calculation + + ITER. SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) DIIS TIME + 1 1.23205200 -0.90035266 -280.35812359 -0.90035266 -0.03569172 0.11D-01 0.52D-02 0 0 25.04 + 2 1.26209544 -0.93132868 -280.38909960 -0.03097601 -0.00482923 0.11D-02 0.13D-02 1 1 30.17 + 3 1.27663639 -0.93174287 -280.38951380 -0.00041420 -0.00170749 0.15D-02 0.20D-03 2 2 37.08 + 4 1.30166877 -0.93808052 -280.39585144 -0.00633765 -0.00062479 0.54D-03 0.76D-04 3 3 43.59 + 5 1.32871740 -0.94131620 -280.39908712 -0.00323568 -0.00025683 0.29D-03 0.24D-04 4 4 49.29 + 6 1.35088814 -0.94287002 -280.40064095 -0.00155382 -0.00008122 0.70D-04 0.14D-04 5 5 54.78 + 7 1.36490071 -0.94369885 -280.40146977 -0.00082882 -0.00002991 0.30D-04 0.51D-05 6 6 60.31 + 8 1.36890653 -0.94381565 -280.40158657 -0.00011680 -0.00001179 0.12D-04 0.15D-05 6 2 65.54 + 9 1.37323469 -0.94411142 -280.40188234 -0.00029577 -0.00000456 0.38D-05 0.85D-06 6 1 71.35 + 10 1.37522516 -0.94418675 -280.40195768 -0.00007533 -0.00000155 0.15D-05 0.24D-06 6 5 76.97 + 11 1.37640249 -0.94423511 -280.40200603 -0.00004835 -0.00000045 0.23D-06 0.12D-06 6 3 82.31 + 12 1.37730675 -0.94427413 -280.40204505 -0.00003902 -0.00000010 0.55D-07 0.26D-07 6 4 88.06 + 13 1.37708019 -0.94424976 -280.40202068 0.00002437 -0.00000003 0.18D-07 0.69D-08 6 6 93.34 + 14 1.37724704 -0.94425633 -280.40202725 -0.00000657 -0.00000001 0.71D-08 0.21D-08 6 5 98.82 + 15 1.37710777 -0.94424614 -280.40201707 0.00001019 -0.00000000 0.21D-08 0.52D-09 6 1 104.76 + 16 1.37711201 -0.94424516 -280.40201608 0.00000099 -0.00000000 0.57D-09 0.29D-09 6 2 110.66 + + Norm of t1 vector: 0.32885530 S-energy: -0.01280677 T1 diagnostic: 0.04469461 + D1 diagnostic: 0.15597653 + D2 diagnostic: 0.18620806 (external, symmetry=2) + Norm of t2 vector: 0.51861952 P-energy: -0.93143838 + Alpha-Beta: -0.71374777 + Alpha-Alpha: -0.10779338 + Beta-Beta: -0.10989724 + + Singles amplitudes (print threshold = 0.500E-01): + + I SYM. A A T(IA) [Beta-Beta] + + 9 1 1 0.21313507 + 12 2 1 0.18784425 + + Doubles amplitudes (print threshold = 0.500E-01): + + I J SYM. A SYM. B A B T(IJ, AB) [Alpha-Beta] + + 11 11 2 2 2 2 -0.10878624 + + Spin contamination 0.00290489 + + Memory could be reduced to 124.69 Mwords without degradation in triples + + + RESULTS + ======= + + Reference energy -279.457770923368 + CABS relaxation correction to RHF -0.002379410418 + New reference energy -279.460150333786 + + F12 corrections for ansatz 3C(FIX) added to UCCSD energy. Coupling mode: 15 + + UCCSD-F12a singles energy -0.012806774336 + UCCSD-F12a pair energy -1.010749252201 + UCCSD-F12a correlation energy -1.023556026537 + Triples (T) contribution -0.048367855962 + Total correlation energy -1.071923882499 + + RHF-UCCSD-F12a energy -280.483706360323 + RHF-UCCSD[T]-F12a energy -280.536901701657 + RHF-UCCSD-T-F12a energy -280.531995546099 + !RHF-UCCSD(T)-F12a energy -280.532074216284 + + F12 corrections for ansatz 3C(FIX) added to UCCSD energy. Coupling mode: 15 + + UCCSD-F12b singles energy -0.012806774336 + UCCSD-F12b pair energy -0.997301909725 + UCCSD-F12b correlation energy -1.010108684060 + Triples (T) contribution -0.048367855962 + Total correlation energy -1.058476540022 + + RHF-UCCSD-F12b energy -280.470259017846 + RHF-UCCSD[T]-F12b energy -280.523454359181 + RHF-UCCSD-T-F12b energy -280.518548203623 + !RHF-UCCSD(T)-F12b energy -280.518626873808 + + Program statistics: + + Available memory in ccsd: 234998504 + Min. memory needed in ccsd: 14322080 + Max. memory used in ccsd: 20521989 + Max. memory used in cckext: 17574048 (17 integral passes) + Max. memory used in cckint: 25718998 ( 1 integral passes) + + + + ********************************************************************************************************************************** + DATASETS * FILE NREC LENGTH (MB) RECORD NAMES + 1 18 29.71 500 610 700 900 950 970 1000 129 960 1100 + VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S + 1400 1410 1200 1210 1080 1600 1650 1700 + T V H0 H01 AOSYM SMH MOLCAS OPER + + 2 5 1.57 700 1000 520 2100 7360 + GEOM BASIS MCVARS RHF F12ABS + + PROGRAMS * TOTAL UCCSD(T) HF-SCF INT + CPU TIMES * 201.38 190.83 4.50 5.79 + REAL TIME * 277.85 SEC + DISK USED * 632.30 MB (local), 7.45 GB (total) + SF USED * 5.22 GB + GA USED * 3.05 MB (max) 0.00 MB (current) + ********************************************************************************************************************************** + + UCCSD(T)-F12/cc-pVTZ-F12 energy= -280.518626873808 + + UCCSD(T)-F12 HF-SCF + -280.51862687 -279.45777092 + ********************************************************************************************************************************** + Molpro calculation terminated From 9d09d2e24cddf0d7aa81c8645a6882cf8e91efb8 Mon Sep 17 00:00:00 2001 From: Alon Grinberg Dana Date: Mon, 19 Aug 2024 09:00:43 +0300 Subject: [PATCH 03/16] Added the .active attr to Species and removed the unused occ attr --- arc/job/factory.py | 1 - arc/species/species.py | 36 +++++++++++++++--------------------- 2 files changed, 15 insertions(+), 22 deletions(-) diff --git a/arc/job/factory.py b/arc/job/factory.py index df3d89a701..4f25d98f92 100644 --- a/arc/job/factory.py +++ b/arc/job/factory.py @@ -141,7 +141,6 @@ def job_factory(job_adapter: str, # shift (str, optional): A string representation alpha- and beta-spin orbitals shifts (molpro only). # use args # is_ts (bool): Whether this species represents a transition structure. Default: ``False``. # use species - # occ (int, optional): The number of occupied orbitals (core + val) from a molpro CCSD sp calc. # number_of_radicals (int, optional): The number of radicals (inputted by the user, ARC won't attempt to # determine it). Defaults to None. Important, e.g., if a Species is a bi-rad # singlet, in which case the job should be unrestricted with diff --git a/arc/species/species.py b/arc/species/species.py index 7c0df39d7c..f85d1d3ec9 100644 --- a/arc/species/species.py +++ b/arc/species/species.py @@ -184,7 +184,15 @@ class ARCSpecies(object): fragments (Optional[List[List[int]]]): Fragments represented by this species, i.e., as in a VdW well or a TS. Entries are atom index lists of all atoms in a fragment, each list represents a different fragment. - occ (int, optional): The number of occupied orbitals (core + val) from a molpro CCSD sp calc. + active (dict, optional): The active orbitals. Possible keys are: + 'occ' (List[int]): The occupied orbitals. + 'closed' (List[int]): The closed-shell orbitals. + 'frozen' (List[int]): The frozen orbitals. + 'core' (List[int]): The core orbitals. + 'e_o' (Tuple[int, int]): The number of active electrons, determined by the total number + of electrons minus the core electrons (2 e's per heavy atom), and the number of active + orbitals, determined by the number of closed-shell orbitals and active orbitals + (w/o core orbitals). irc_label (str, optional): The label of an original ``ARCSpecies`` object (a TS) for which an IRC job was spawned. The present species object instance represents a geometry optimization job of the IRC result in one direction. @@ -286,7 +294,7 @@ class ARCSpecies(object): fragments (Optional[List[List[int]]]): Fragments represented by this species, i.e., as in a VdW well or a TS. Entries are atom index lists of all atoms in a fragment, each list represents a different fragment. - occ (int): The number of occupied orbitals (core + val) from a molpro CCSD sp calc. + active (dict): The active orbitals. irc_label (str): The label of an original ``ARCSpecies`` object (a TS) for which an IRC job was spawned. The present species object instance represents a geometry optimization job of the IRC result in one direction. If a species is a transition state, then this attribute contains the @@ -297,6 +305,7 @@ class ARCSpecies(object): """ def __init__(self, + active: Optional[dict] = None, adjlist: str = '', bdes: Optional[list] = None, bond_corrections: Optional[dict] = None, @@ -318,7 +327,6 @@ def __init__(self, multiplicity: Optional[int] = None, multi_species: Optional[str] = None, number_of_radicals: Optional[int] = None, - occ: Optional[int] = None, optical_isomers: Optional[int] = None, preserve_param_in_scan: Optional[list] = None, rmg_species: Optional[Species] = None, @@ -357,7 +365,7 @@ def __init__(self, self.number_of_radicals = number_of_radicals self.external_symmetry = external_symmetry self.irc_label = irc_label - self.occ = occ + self.active = active self.optical_isomers = optical_isomers self.charge = charge self.run_time = run_time @@ -734,8 +742,8 @@ def as_dict(self, species_dict['zmat'] = self.zmat if self.checkfile is not None: species_dict['checkfile'] = self.checkfile - if self.occ is not None: - species_dict['occ'] = self.occ + if self.active is not None: + species_dict['active'] = self.active if self.most_stable_conformer is not None: species_dict['most_stable_conformer'] = self.most_stable_conformer if self.cheap_conformer is not None: @@ -793,7 +801,7 @@ def from_dict(self, species_dict): self.e_elect = species_dict['e_elect'] if 'e_elect' in species_dict else None self.e0 = species_dict['e0'] if 'e0' in species_dict else None self.tsg_spawned = species_dict['tsg_spawned'] if 'tsg_spawned' in species_dict else False - self.occ = species_dict['occ'] if 'occ' in species_dict else None + self.active = species_dict['active'] if 'active' in species_dict else None self.arkane_file = species_dict['arkane_file'] if 'arkane_file' in species_dict else None self.yml_path = species_dict['yml_path'] if 'yml_path' in species_dict else None self.rxn_label = species_dict['rxn_label'] if 'rxn_label' in species_dict else None @@ -2335,20 +2343,6 @@ def tok(self): self.execution_time = datetime.datetime.now() - self.t0 -def determine_occ(xyz, charge): - """ - Determines the number of occupied orbitals for an MRCI calculation. - - Todo - """ - electrons = 0 - for line in xyz.split('\n'): - if line: - atom = Atom(element=str(line.split()[0])) - electrons += atom.number - electrons -= charge - - def determine_rotor_symmetry(label: str, pivots: Union[List[int], str], rotor_path: str = '', From fcc12b0ad9086ecf924e480bfb5f339a73d27c54 Mon Sep 17 00:00:00 2001 From: Alon Grinberg Dana Date: Mon, 19 Aug 2024 13:34:28 +0300 Subject: [PATCH 04/16] Added MRCI to Orca's adapter --- arc/job/adapters/orca.py | 32 ++++++++++++++++++++++---------- 1 file changed, 22 insertions(+), 10 deletions(-) diff --git a/arc/job/adapters/orca.py b/arc/job/adapters/orca.py index e118db214e..17e151e732 100644 --- a/arc/job/adapters/orca.py +++ b/arc/job/adapters/orca.py @@ -50,17 +50,16 @@ !${job_type_1} ${job_type_2} %%maxcore ${memory} -%%pal # job parallelization settings -nprocs ${cpus} -end -%%scf # recommended SCF settings -MaxIter 500 -end${scan} -${block} +%%pal nprocs ${cpus} end * xyz ${charge} ${multiplicity} ${xyz} * + +%%scf +MaxIter 999 +end${scan} +${block} """ @@ -225,7 +224,7 @@ def write_input_file(self) -> None: input_dict['cpus'] = self.cpu_cores input_dict['label'] = self.species_label input_dict['memory'] = self.input_file_memory - input_dict['method'] = self.level.method + input_dict['method'] = self.level.method if 'mrci' not in self.level.method else '' input_dict['multiplicity'] = self.multiplicity input_dict['xyz'] = xyz_to_str(self.xyz) @@ -295,6 +294,19 @@ def write_input_file(self) -> None: elif self.job_type == 'sp': input_dict['job_type_1'] = 'sp' + if 'mrci' in self.level.method and self.species[0].active is not None: + if '_' in self.level.method: + methods = self.level.method.split('_') + block = '' + for method in methods: + if method == 'mp2': + block += '\n\n%mp2\n RI true\nend' + elif method == 'casscf': + block += (f'\n\n%casscf\n nel {self.species[0].active[0]}' + f'\n norb {self.species[0].active[1]}\n nroots 1\n maxiter 999\nend') + elif method == 'mrci': + block += f'\n\n%mrci\n citype MRCI\n davidsonopt true\n maxiter 999\nend\n' + input_dict['block'] += block elif self.job_type == 'scan': scans, torsion_strings = list(), list() @@ -322,12 +334,12 @@ def write_input_file(self) -> None: %cpcm SMD true SMDsolvent "{self.level.solvent}" end - """, +""", key1='block') elif self.level.solvation_method.lower() in ['pcm', 'cpcm']: self.add_to_args(val=f""" !CPCM({self.level.solvent}) - """, +""", key1='block') input_dict = update_input_dict_with_args(args=self.args, input_dict=input_dict) From 47571d342d40b24dac433f2723ca4711bd9ed22b Mon Sep 17 00:00:00 2001 From: Alon Grinberg Dana Date: Mon, 19 Aug 2024 13:34:52 +0300 Subject: [PATCH 05/16] Tests: Creating input files in Orca --- arc/job/adapters/orca_test.py | 109 +++++++++++++++++++++++++--------- 1 file changed, 82 insertions(+), 27 deletions(-) diff --git a/arc/job/adapters/orca_test.py b/arc/job/adapters/orca_test.py index e8663c85b7..a09bb8c4e2 100644 --- a/arc/job/adapters/orca_test.py +++ b/arc/job/adapters/orca_test.py @@ -69,6 +69,20 @@ def setUpClass(cls): H -0.53338088 -0.77135867 -0.54806440""")], testing=True, ) + cls.job_4 = OrcaAdapter(execution_type='queue', + job_type='sp', + level=Level(method='MP2_CASSCF_MRCI', basis='aug-cc-pVTZ'), + project='test4', + project_directory=os.path.join(ARC_PATH, 'arc', 'testing', 'test_OrcaAdapter'), + species=[ARCSpecies(label='CH3O', + active=(14, 7), + xyz="""C 0.03807240 0.00035621 -0.00484242 + O 1.35198769 0.01264937 -0.17195885 + H -0.33965241 -0.14992727 1.02079480 + H -0.51702680 0.90828035 -0.29592912 + H -0.53338088 -0.77135867 -0.54806440""")], + testing=True, + ) def test_set_cpu_and_mem(self): """Test assigning number of cpu's and memory""" self.job_1.input_file_memory = None @@ -90,13 +104,7 @@ def test_write_input_file(self): !sp %maxcore 1792 -%pal # job parallelization settings -nprocs 8 -end -%scf # recommended SCF settings -MaxIter 500 -end - +%pal nprocs 8 end * xyz 0 2 C 0.03807240 0.00035621 -0.00484242 @@ -105,6 +113,11 @@ def test_write_input_file(self): H -0.51702680 0.90828035 -0.29592912 H -0.53338088 -0.77135867 -0.54806440 * + +%scf +MaxIter 999 +end + """ self.assertEqual(content_1, job_1_expected_input_file) @@ -117,19 +130,7 @@ def test_write_input_file_with_SMD_solvation(self): !sp %maxcore 1792 -%pal # job parallelization settings -nprocs 8 -end -%scf # recommended SCF settings -MaxIter 500 -end - - - -%cpcm SMD true - SMDsolvent "dmso" -end - +%pal nprocs 8 end * xyz 0 2 C 0.03807240 0.00035621 -0.00484242 @@ -138,6 +139,17 @@ def test_write_input_file_with_SMD_solvation(self): H -0.51702680 0.90828035 -0.29592912 H -0.53338088 -0.77135867 -0.54806440 * + +%scf +MaxIter 999 +end + + + +%cpcm SMD true + SMDsolvent "dmso" +end + """ self.assertEqual(content_2, job_2_expected_input_file) @@ -151,17 +163,37 @@ def test_write_input_file_with_CPCM_solvation(self): !sp %maxcore 1792 -%pal # job parallelization settings -nprocs 8 -end -%scf # recommended SCF settings -MaxIter 500 +%pal nprocs 8 end + +* xyz 0 2 +C 0.03807240 0.00035621 -0.00484242 +O 1.35198769 0.01264937 -0.17195885 +H -0.33965241 -0.14992727 1.02079480 +H -0.51702680 0.90828035 -0.29592912 +H -0.53338088 -0.77135867 -0.54806440 +* + +%scf +MaxIter 999 end !CPCM(water) - + +""" + self.assertEqual(content_3, job_3_expected_input_file) + + def test_write_input_file_mrci(self): + """Test writing Orca input files""" + self.job_4.write_input_file() + with open(os.path.join(self.job_4.local_path, input_filenames[self.job_4.job_adapter]), 'r') as f: + content_4 = f.read() + job_4_expected_input_file = """!uHF aug-cc-pvtz tightscf +!sp + +%maxcore 1792 +%pal nprocs 8 end * xyz 0 2 C 0.03807240 0.00035621 -0.00484242 @@ -170,8 +202,31 @@ def test_write_input_file_with_CPCM_solvation(self): H -0.51702680 0.90828035 -0.29592912 H -0.53338088 -0.77135867 -0.54806440 * + +%scf +MaxIter 999 +end + + +%mp2 + RI true +end + +%casscf + nel 14 + norb 7 + nroots 1 + maxiter 999 +end + +%mrci + citype MRCI + davidsonopt true + maxiter 999 +end + """ - self.assertEqual(content_3, job_3_expected_input_file) + self.assertEqual(content_4, job_4_expected_input_file) def test_set_files(self): """Test setting files""" From 15eb72d93951bd9e46ee0c0fe1f4f6422477ea05 Mon Sep 17 00:00:00 2001 From: Alon Grinberg Dana Date: Mon, 19 Aug 2024 13:35:16 +0300 Subject: [PATCH 06/16] MRCI modifications in Molpro's adapter --- arc/job/adapters/molpro.py | 57 ++++++++++++++++++-------------------- 1 file changed, 27 insertions(+), 30 deletions(-) diff --git a/arc/job/adapters/molpro.py b/arc/job/adapters/molpro.py index 176570aa94..9b6e3b7820 100644 --- a/arc/job/adapters/molpro.py +++ b/arc/job/adapters/molpro.py @@ -8,12 +8,10 @@ import math import os from typing import TYPE_CHECKING, List, Optional, Tuple, Union -import socket from mako.template import Template from arc.common import get_logger -from arc.exceptions import JobError from arc.imports import incore_commands, settings from arc.job.adapter import JobAdapter from arc.job.adapters.common import (_initialize_adapter, @@ -37,7 +35,7 @@ settings['output_filenames'], settings['servers'], settings['submit_filenames'] input_template = """***,${label} -memory,${memory},m; +memory,Total=${memory},m; geometry={angstrom; ${xyz}} @@ -48,8 +46,8 @@ ${cabs} int; {hf;${shift} -maxit,1000; -wf,spin=${spin},charge=${charge};} + maxit,999; + wf,spin=${spin},charge=${charge};} ${restricted}${method}; @@ -252,20 +250,26 @@ def write_input_file(self) -> None: keywords.append('ORBITAL,IGNORE_ERROR') if 'mrci' in self.level.method: - if self.species[0].occ > 16: - raise JobError(f'Will not execute an MRCI calculation with more than 16 occupied orbitals ' - f'(got {self.species[0].occ}).\n' - f'Selective occ, closed, core, frozen keyword still not implemented.') input_dict['orbitals'] = '\ngprint,orbitals;\n' + input_dict['restricted'] = '' + if '_' in self.level.method: + methods = self.level.method.split('_') + input_dict['method'] = '' + for method in methods: + input_dict['method'] += '\n\n{' + method.lower() + ';\n' + if 'mp2' not in method.lower(): + input_dict['method'] += ' maxit,999;\n' + input_dict['method'] += f' wf,spin={input_dict["spin"]},charge={input_dict["charge"]};' + '}' + else: + input_dict['method'] = f"""{{casscf; + maxit,999; + wf,spin={input_dict['spin']},charge={input_dict['charge']};}} + +{{mrci{"-f12" if "f12" in self.level.method.lower() else ""}; + maxit,999; + wf,spin={input_dict['spin']},charge={input_dict['charge']};}}""" + input_dict['block'] += '\n\nE_mrci=energy;\nE_mrci_Davidson=energd;\n\ntable,E_mrci,E_mrci_Davidson;' - input_dict['method'] = input_dict['rerstricted'] = '' - input_dict['shift'] = 'shift,-1.0,-0.5;' - input_dict['job_type_1'] = f"""{{multi; -{self.species[0].occ}noextra,failsafe,config,csf; -wf,spin={input_dict['spin']},charge={input_dict['charge']}; -natorb,print,ci;}}""" - input_dict['job_type_2'] = f"""{{mrci; -${self.species[0].occ}wf,spin=${input_dict['spin']},charge=${input_dict['charge']};}}""" input_dict = update_input_dict_with_args(args=self.args, input_dict=input_dict) @@ -325,19 +329,12 @@ def set_input_file_memory(self) -> None: """ Set the input_file_memory attribute. """ - # Molpro's memory is per cpu core and in MW (mega word; 1000 MW = 7.45 GB on a 64-bit machine) - # The conversion from mW to GB was done using this (https://deviceanalytics.com/words-to-bytes-converter/) - # specifying a 64-bit architecture. - # - # See also: - # https://www.molpro.net/pipermail/molpro-user/2010-April/003723.html - # In the link, they describe the conversion of 100,000,000 Words (100Mword) is equivalent to - # 800,000,000 bytes (800 mb). - # Formula - (100,000,000 [Words]/( 800,000,000 [Bytes] / (job mem in gb * 1000,000,000 [Bytes])))/ 1000,000 [Words -> MegaWords] - # The division by 1E6 is for converting into MWords - # Due to Zeus's configuration, there is only 1 nproc so the memory should not be divided by cpu_cores. - self.input_file_memory = math.ceil(self.job_memory_gb / (7.45e-3 * self.cpu_cores)) if 'zeus' not in socket.gethostname() else math.ceil(self.job_memory_gb / (7.45e-3)) - + # Molpro's memory is per cpu core, but here we ask for Total memory. + # Molpro measures memory in MW (mega word; 1000 MW = 7.45 GB on a 64-bit machine) + # The conversion from mW to GB was done using https://www.molpro.net/manual/doku.php?id=general_program_structure#memory_option_in_command_line + # 3.2 GB = 100 mw (case sensitive) total (as in this implimentation) -> 31.25 mw/GB is the conversion rate + self.input_file_memory = math.ceil(self.job_memory_gb * 31.25) + def execute_incore(self): """ Execute a job incore. From 192f679885c16136ae61992f38f519dedb12aa57 Mon Sep 17 00:00:00 2001 From: Alon Grinberg Dana Date: Mon, 19 Aug 2024 13:43:23 +0300 Subject: [PATCH 07/16] MRCI treatment in Scheduler --- arc/scheduler.py | 53 +++++++++++++----------------------------------- 1 file changed, 14 insertions(+), 39 deletions(-) diff --git a/arc/scheduler.py b/arc/scheduler.py index dbaef49b1c..7a6a9ce841 100644 --- a/arc/scheduler.py +++ b/arc/scheduler.py @@ -1256,16 +1256,14 @@ def run_sp_job(self, level: Optional[Level] = None, ): """ - Spawn a single point job using 'final_xyz' for species ot TS 'label'. - If the method is MRCI, first spawn a simple CCSD job, and use orbital determination to run the MRCI job. + Spawn a single point job using 'final_xyz' for species or a TS represented by 'label'. + If the method is MRCI, first spawn a simple CCSD(T) job, and use orbital determination to run the MRCI job. Args: label (str): The species label. level (Level): An alternative level of theory to run at. If ``None``, self.sp_level will be used. """ level = level or self.sp_level - - # determine_occ(xyz=self.xyz, charge=self.charge) if level == self.opt_level and not self.composite_method \ and not (level.software == 'xtb' and self.species_dict[label].is_ts) \ and 'paths' in self.output[label] and 'geo' in self.output[label]['paths'] \ @@ -1283,57 +1281,33 @@ def run_sp_job(self, sp_path=os.path.join(recent_opt_job.local_path_to_output_file), level=level, ) - # If opt is not in the job dictionary, the likely explanation is this job has been restarted elif 'geo' in self.output[label]['paths']: # Then just use this path directly self.post_sp_actions(label=label, sp_path=self.output[label]['paths']['geo'], level=level, ) - else: raise RuntimeError(f'Unable to set the path for the sp job for species {label}') - return - if 'sp' not in self.job_dict[label].keys(): # Check whether single-point energy jobs have been spawned yet. - # We're spawning the first sp job for this species. + + if 'sp' not in self.job_dict[label].keys(): self.job_dict[label]['sp'] = dict() if self.composite_method: raise SchedulerError(f'run_sp_job() was called for {label} which has a composite method level of theory') if 'mrci' in level.method: if self.job_dict[label]['sp']: - # Parse orbital information from the CCSD job, then run MRCI - job0 = None - job_name_0 = 0 - for job_name, job in self.job_dict[label]['sp'].items(): - if int(job_name.split('_a')[-1]) > job_name_0: - job_name_0 = int(job_name.split('_a')[-1]) - job0 = job - with open(job0.local_path_to_output_file, 'r') as f: - lines = f.readlines() - core = val = 0 - for line in lines: - if 'NUMBER OF CORE ORBITALS' in line: - core = int(line.split()[4]) - elif 'NUMBER OF VALENCE ORBITALS' in line: - val = int(line.split()[4]) - if val * core: - break - else: - raise SchedulerError(f'Could not determine number of core and valence orbitals from CCSD ' - f'sp calculation for {label}') - self.species_dict[label].occ = val + core # the occupied orbitals are the core and valence orbitals - self.run_job(label=label, - xyz=self.species_dict[label].get_xyz(generate=False), - level_of_theory='ccsd/vdz', - job_type='sp') + if self.species_dict[label].active is None: + self.species_dict[label].active = parser.parse_active_space( + sp_path=self.output[label]['paths']['sp'], + species=self.species_dict[label]) else: - # MRCI was requested but no sp job ran for this species, run CCSD first - logger.info(f'running a CCSD job for {label} before MRCI') + logger.info(f'Running a CCSD/cc-pVDZ job for {label} before the MRCI job') self.run_job(label=label, xyz=self.species_dict[label].get_xyz(generate=False), - level_of_theory='ccsd/vdz', + level_of_theory='ccsd/cc-pvdz', job_type='sp') + return if self.job_types['sp']: if self.species_dict[label].multi_species: if self.output_multi_spc[self.species_dict[label].multi_species].get('sp', False): @@ -2656,7 +2630,7 @@ def check_sp_job(self, job (JobAdapter): The single point job object. """ if 'mrci' in self.sp_level.method and job.level is not None and 'mrci' not in job.level.method: - # This is a CCSD job ran before MRCI. Spawn MRCI + self.output[label]['paths']['sp'] = job.local_path_to_output_file self.run_sp_job(label) elif job.job_status[1]['status'] == 'done': self.post_sp_actions(label, @@ -2691,6 +2665,8 @@ def post_sp_actions(self, self.output[label]['paths']['sp'] = sp_path if self.sp_level is not None and 'ccsd' in self.sp_level.method: self.species_dict[label].t1 = parser.parse_t1(self.output[label]['paths']['sp']) + self.species_dict[label].active = parser.parse_active_space(sp_path=self.output[label]['paths']['sp'], + species=self.species_dict[label]) zpe_scale_factor = 0.99 if (self.composite_method is not None and 'cbs-qb3' in self.composite_method.method) \ else 1.0 self.species_dict[label].e_elect = parser.parse_e_elect(self.output[label]['paths']['sp'], @@ -2715,7 +2691,6 @@ def post_sp_actions(self, self.run_sp_job(label=label, level=solvation_sp_level) self.run_sp_job(label=label, level=self.sp_level.solvation_scheme_level) else: - # this is one of the additional sp jobs spawned by the above previously if level is not None and level.solvation_method is not None: self.output[label]['paths']['sp_sol'] = sp_path else: From e617632b84cbcadc34697a6a4c6e0867cd9fca79 Mon Sep 17 00:00:00 2001 From: Alon Grinberg Dana Date: Mon, 19 Aug 2024 15:06:55 +0300 Subject: [PATCH 08/16] Fix Orca determine_ess_status scf_energy_initial_iteration was referenced before assignment --- arc/job/trsh.py | 32 ++++++++++++++++++-------------- 1 file changed, 18 insertions(+), 14 deletions(-) diff --git a/arc/job/trsh.py b/arc/job/trsh.py index 04995c41f2..5115a29d48 100644 --- a/arc/job/trsh.py +++ b/arc/job/trsh.py @@ -263,6 +263,7 @@ def determine_ess_status(output_path: str, done = False for i, line in enumerate(reverse_lines): if 'ORCA TERMINATED NORMALLY' in line: + scf_energy_initial_iteration = None # not done yet, things can still go wrong (e.g., SCF energy might blow up) for j, info in enumerate(forward_lines): if 'Starting incremental Fock matrix formation' in info: @@ -273,21 +274,24 @@ def determine_ess_status(output_path: str, # this value is very close to the scf energy at last iteration and is easier to parse scf_energy_last_iteration = float(forward_lines[j + 3].split()[3]) break - # Check if final SCF energy makes sense - scf_energy_ratio = scf_energy_last_iteration / scf_energy_initial_iteration - scf_energy_ratio_threshold = 2 # it is rare that this ratio > 2 - if scf_energy_ratio > scf_energy_ratio_threshold: - keywords = ['SCF'] - error = f'The SCF energy seems diverged during iterations. SCF energy after initial ' \ - f'iteration is {scf_energy_initial_iteration}. SCF energy after final iteration ' \ - f'is {scf_energy_last_iteration}. The ratio between final and initial SCF energy ' \ - f'is {scf_energy_ratio}. This ratio is greater than the default threshold of ' \ - f'{scf_energy_ratio_threshold}. Please consider using alternative methods or larger ' \ - f'basis sets.' - line = '' - else: + if scf_energy_initial_iteration is not None: + # Check if final SCF energy makes sense + scf_energy_ratio = scf_energy_last_iteration / scf_energy_initial_iteration + scf_energy_ratio_threshold = 2 # it is rare that this ratio > 2 + if scf_energy_ratio > scf_energy_ratio_threshold: + keywords = ['SCF'] + error = f'The SCF energy seems diverged during iterations. SCF energy after initial ' \ + f'iteration is {scf_energy_initial_iteration}. SCF energy after final iteration ' \ + f'is {scf_energy_last_iteration}. The ratio between final and initial SCF energy ' \ + f'is {scf_energy_ratio}. This ratio is greater than the default threshold of ' \ + f'{scf_energy_ratio_threshold}. Please consider using alternative methods or larger ' \ + f'basis sets.' + line = '' + else: + done = True + break + if scf_energy_initial_iteration is None: done = True - break elif 'ORCA finished by error termination in SCF' in line: keywords = ['SCF'] for j, info in enumerate(reverse_lines): From dd0e4c4f3a662b1c898a98c2a0f267f8d236f380 Mon Sep 17 00:00:00 2001 From: Alon Grinberg Dana Date: Mon, 19 Aug 2024 15:21:52 +0300 Subject: [PATCH 09/16] Tests: Detect successful MRCI run in Orca --- arc/job/trsh_test.py | 8 + arc/testing/trsh/orca/O2_MRCI.log | 2165 +++++++++++++++++++++++++++++ 2 files changed, 2173 insertions(+) create mode 100644 arc/testing/trsh/orca/O2_MRCI.log diff --git a/arc/job/trsh_test.py b/arc/job/trsh_test.py index e5d9964989..689fe0a72b 100644 --- a/arc/job/trsh_test.py +++ b/arc/job/trsh_test.py @@ -181,6 +181,14 @@ def test_determine_ess_status(self): self.assertEqual(keywords, list()) self.assertEqual(error, "") self.assertEqual(line, "") + path = os.path.join(self.base_path["orca"], "O2_MRCI.log") + status, keywords, error, line = trsh.determine_ess_status( + output_path=path, species_label="test", job_type="sp", software="orca" + ) + self.assertEqual(status, "done") + self.assertEqual(keywords, list()) + self.assertEqual(error, "") + self.assertEqual(line, "") # test detection of a successful job # notice that the log file in this example has a different format under the line diff --git a/arc/testing/trsh/orca/O2_MRCI.log b/arc/testing/trsh/orca/O2_MRCI.log new file mode 100644 index 0000000000..0fe72aab7a --- /dev/null +++ b/arc/testing/trsh/orca/O2_MRCI.log @@ -0,0 +1,2165 @@ + + ***************** + * O R C A * + ***************** + + #, + ### + #### + ##### + ###### + ########, + ,,################,,,,, + ,,#################################,, + ,,##########################################,, + ,#########################################, ''#####, + ,#############################################,, '####, + ,##################################################,,,,####, + ,###########'''' ''''############################### + ,#####'' ,,,,##########,,,, '''####''' '#### + ,##' ,,,,###########################,,, '## + ' ,,###'''' '''############,,, + ,,##'' '''############,,,, ,,,,,,###'' + ,#'' '''#######################''' + ' ''''####'''' + ,#######, #######, ,#######, ## + ,#' '#, ## ## ,#' '#, #''# ###### ,####, + ## ## ## ,#' ## #' '# # #' '# + ## ## ####### ## ,######, #####, # # + '#, ,#' ## ## '#, ,#' ,# #, ## #, ,# + '#######' ## ## '#######' #' '# #####' # '####' + + + + ####################################################### + # -***- # + # Department of theory and spectroscopy # + # Directorship and core code : Frank Neese # + # Max Planck Institute fuer Kohlenforschung # + # Kaiser Wilhelm Platz 1 # + # D-45470 Muelheim/Ruhr # + # Germany # + # # + # All rights reserved # + # -***- # + ####################################################### + + + Program Version 5.0.4 - RELEASE - + + + With contributions from (in alphabetic order): + Daniel Aravena : Magnetic Suceptibility + Michael Atanasov : Ab Initio Ligand Field Theory (pilot matlab implementation) + Alexander A. Auer : GIAO ZORA, VPT2 properties, NMR spectrum + Ute Becker : Parallelization + Giovanni Bistoni : ED, misc. LED, open-shell LED, HFLD + Martin Brehm : Molecular dynamics + Dmytro Bykov : SCF Hessian + Vijay G. Chilkuri : MRCI spin determinant printing, contributions to CSF-ICE + Dipayan Datta : RHF DLPNO-CCSD density + Achintya Kumar Dutta : EOM-CC, STEOM-CC + Dmitry Ganyushin : Spin-Orbit,Spin-Spin,Magnetic field MRCI + Miquel Garcia : C-PCM and meta-GGA Hessian, CC/C-PCM, Gaussian charge scheme + Yang Guo : DLPNO-NEVPT2, F12-NEVPT2, CIM, IAO-localization + Andreas Hansen : Spin unrestricted coupled pair/coupled cluster methods + Benjamin Helmich-Paris : MC-RPA, TRAH-SCF, COSX integrals + Lee Huntington : MR-EOM, pCC + Robert Izsak : Overlap fitted RIJCOSX, COSX-SCS-MP3, EOM + Marcus Kettner : VPT2 + Christian Kollmar : KDIIS, OOCD, Brueckner-CCSD(T), CCSD density, CASPT2, CASPT2-K + Simone Kossmann : Meta GGA functionals, TD-DFT gradient, OOMP2, MP2 Hessian + Martin Krupicka : Initial AUTO-CI + Lucas Lang : DCDCAS + Marvin Lechner : AUTO-CI (C++ implementation), FIC-MRCC + Dagmar Lenk : GEPOL surface, SMD + Dimitrios Liakos : Extrapolation schemes; Compound Job, initial MDCI parallelization + Dimitrios Manganas : Further ROCIS development; embedding schemes + Dimitrios Pantazis : SARC Basis sets + Anastasios Papadopoulos: AUTO-CI, single reference methods and gradients + Taras Petrenko : DFT Hessian,TD-DFT gradient, ASA, ECA, R-Raman, ABS, FL, XAS/XES, NRVS + Peter Pinski : DLPNO-MP2, DLPNO-MP2 Gradient + Christoph Reimann : Effective Core Potentials + Marius Retegan : Local ZFS, SOC + Christoph Riplinger : Optimizer, TS searches, QM/MM, DLPNO-CCSD(T), (RO)-DLPNO pert. Triples + Tobias Risthaus : Range-separated hybrids, TD-DFT gradient, RPA, STAB + Michael Roemelt : Original ROCIS implementation + Masaaki Saitow : Open-shell DLPNO-CCSD energy and density + Barbara Sandhoefer : DKH picture change effects + Avijit Sen : IP-ROCIS + Kantharuban Sivalingam : CASSCF convergence, NEVPT2, FIC-MRCI + Bernardo de Souza : ESD, SOC TD-DFT + Georgi Stoychev : AutoAux, RI-MP2 NMR, DLPNO-MP2 response + Willem Van den Heuvel : Paramagnetic NMR + Boris Wezisla : Elementary symmetry handling + Frank Wennmohs : Technical directorship + + + We gratefully acknowledge several colleagues who have allowed us to + interface, adapt or use parts of their codes: + Stefan Grimme, W. Hujo, H. Kruse, P. Pracht, : VdW corrections, initial TS optimization, + C. Bannwarth, S. Ehlert DFT functionals, gCP, sTDA/sTD-DF + Ed Valeev, F. Pavosevic, A. Kumar : LibInt (2-el integral package), F12 methods + Garnet Chan, S. Sharma, J. Yang, R. Olivares : DMRG + Ulf Ekstrom : XCFun DFT Library + Mihaly Kallay : mrcc (arbitrary order and MRCC methods) + Jiri Pittner, Ondrej Demel : Mk-CCSD + Frank Weinhold : gennbo (NPA and NBO analysis) + Christopher J. Cramer and Donald G. Truhlar : smd solvation model + Lars Goerigk : TD-DFT with DH, B97 family of functionals + V. Asgeirsson, H. Jonsson : NEB implementation + FAccTs GmbH : IRC, NEB, NEB-TS, DLPNO-Multilevel, CI-OPT + MM, QMMM, 2- and 3-layer-ONIOM, Crystal-QMMM, + LR-CPCM, SF, NACMEs, symmetry and pop. for TD-DFT, + nearIR, NL-DFT gradient (VV10), updates on ESD, + ML-optimized integration grids + S Lehtola, MJT Oliveira, MAL Marques : LibXC Library + Liviu Ungur et al : ANISO software + + + Your calculation uses the libint2 library for the computation of 2-el integrals + For citations please refer to: http://libint.valeyev.net + + Your ORCA version has been built with support for libXC version: 5.1.0 + For citations please refer to: https://tddft.org/programs/libxc/ + + This ORCA versions uses: + CBLAS interface : Fast vector & matrix operations + LAPACKE interface : Fast linear algebra routines + SCALAPACK package : Parallel linear algebra routines + Shared memory : Shared parallel matrices + BLAS/LAPACK : OpenBLAS 0.3.15 USE64BITINT DYNAMIC_ARCH NO_AFFINITY Zen SINGLE_THREADED + Core in use : Zen + Copyright (c) 2011-2014, The OpenBLAS Project + + +================================================================================ + +----- Orbital basis set information ----- +Your calculation utilizes the basis: aug-cc-pVTZ + H, B-Ne : Obtained from the ccRepo (grant-hill.group.shef.ac.uk/ccrepo) Feb. 2017 + R. A. Kendall, T. H. Dunning, Jr., R. J. Harrison, J. Chem. Phys. 96, 6796 (1992) + He : Obtained from the ccRepo (grant-hill.group.shef.ac.uk/ccrepo) Feb. 2017 + D. E. Woon, T. H. Dunning, Jr., J. Chem. Phys. 100, 2975 (1994) + Li-Be, Na : Obtained from the ccRepo (grant-hill.group.shef.ac.uk/ccrepo) Feb. 2017 + B. P. Prascher, D. E. Woon, K. A. Peterson, T. H. Dunning, Jr., A. K. Wilson, Theor. Chem. Acc. 128, 69 (2011) + Mg : Obtained from the Peterson Research Group Website (tyr0.chem.wsu.edu/~kipeters) Feb. 2017 + B. P. Prascher, D. E. Woon, K. A. Peterson, T. H. Dunning, Jr., A. K. Wilson, Theor. Chem. Acc. 128, 69 (2011) + Al-Ar : Obtained from the ccRepo (grant-hill.group.shef.ac.uk/ccrepo) Feb. 2017 + D. E. Woon, T. H. Dunning, Jr., J. Chem. Phys. 98, 1358 (1993) + Sc-Zn : Obtained from the ccRepo (grant-hill.group.shef.ac.uk/ccrepo) Feb. 2017 + N. B. Balabanov, K. A. Peterson, J. Chem. Phys. 123, 064107 (2005) + N. B. Balabanov, K. A. Peterson, J. Chem. Phys. 125, 074110 (2006) + Ga-Kr : Obtained from the ccRepo (grant-hill.group.shef.ac.uk/ccrepo) Feb. 2017 + A. K. Wilson, D. E. Woon, K. A. Peterson, T. H. Dunning, Jr., J. Chem. Phys. 110, 7667 (1999) + Ag, Au : Obtained from the Peterson Research Group Website (tyr0.chem.wsu.edu/~kipeters) Feb. 2017 + K. A. Peterson, C. Puzzarini, Theor. Chem. Acc. 114, 283 (2005) + +================================================================================ + WARNINGS + Please study these warnings very carefully! +================================================================================ + + +INFO : the flag for use of the SHARK integral package has been found! + +================================================================================ + INPUT FILE +================================================================================ +NAME = input.in +| 1> !uHF aug-cc-pvtz tightscf +| 2> !sp +| 3> +| 4> %maxcore 3200 +| 5> %pal nprocs 16 end +| 6> +| 7> * xyz 0 3 +| 8> O 0.00000000 0.00000000 0.60765400 +| 9> O 0.00000000 0.00000000 -0.60765400 +| 10> * +| 11> +| 12> %scf +| 13> MaxIter 999 +| 14> end +| 15> +| 16> +| 17> %mp2 +| 18> RI true +| 19> end +| 20> +| 21> %casscf +| 22> nel 12 +| 23> norb 7 +| 24> nroots 1 +| 25> maxiter 999 +| 26> end +| 27> +| 28> %mrci +| 29> citype MRCI +| 30> davidsonopt true +| 31> maxiter 999 +| 32> end +| 33> +| 34> +| 35> ****END OF INPUT**** +================================================================================ + + **************************** + * Single Point Calculation * + **************************** + +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + O 0.000000 0.000000 0.607654 + O 0.000000 0.000000 -0.607654 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 O 8.0000 0 15.999 0.000000 0.000000 1.148300 + 1 O 8.0000 0 15.999 0.000000 0.000000 -1.148300 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 1.215308000000 0.00000000 0.00000000 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + O 0 0 0 0.000000000000 0.00000000 0.00000000 + O 1 0 0 2.296599288364 0.00000000 0.00000000 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 1 groups of distinct atoms + + Group 1 Type O : 19s6p3d2f contracted to 5s4p3d2f pattern {88111/3111/111/11} + +Atom 0O basis set group => 1 +Atom 1O basis set group => 1 + + + ************************************************************ + * Program running with 16 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA GTO INTEGRAL CALCULATION +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021 +------------------------------------------------------------------------------ + + +Reading SHARK input file input.SHARKINP.tmp ... ok +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 2 +Number of basis functions ... 104 +Number of shells ... 40 +Maximum angular momentum ... 3 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... PARTIAL GENERAL contraction +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Finite Nucleus Model ... NOT USED +Auxiliary Coulomb fitting basis ... NOT available +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available +Integral threshold ... 2.500000e-11 +Primitive cut-off ... 2.500000e-12 +Primitive pair pre-selection threshold ... 2.500000e-12 + +Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 40 +Calculating pre-screening integrals (ORCA) ... done ( 0.1 sec) Dimension = 28 +Organizing shell pair data ... done ( 0.7 sec) +Shell pair information +Total number of shell pairs ... 820 +Shell pairs after pre-screening ... 774 +Total number of primitive shell pairs ... 996 +Primitive shell pairs kept ... 925 + la=0 lb=0: 207 shell pairs + la=1 lb=0: 176 shell pairs + la=1 lb=1: 36 shell pairs + la=2 lb=0: 132 shell pairs + la=2 lb=1: 48 shell pairs + la=2 lb=2: 21 shell pairs + la=3 lb=0: 88 shell pairs + la=3 lb=1: 32 shell pairs + la=3 lb=2: 24 shell pairs + la=3 lb=3: 10 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 27.867290704249 Eh + +SHARK setup successfully completed in 2.5 seconds + +Maximum memory used throughout the entire GTOINT-calculation: 16.5 MB + + + ************************************************************ + * Program running with 16 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA SCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... CASSCF + Total Charge Charge .... 0 + Multiplicity Mult .... 3 + Number of Electrons NEL .... 16 + Basis Dimension Dim .... 92 + Nuclear Repulsion ENuc .... 27.8672907042 Eh + + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.466e-04 +Time for diagonalization ... 0.002 sec +Threshold for overlap eigenvalues ... 1.000e-08 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.001 sec +Total time needed ... 0.003 sec + +Time for model grid setup = 0.014 sec + +------------------------------ +INITIAL GUESS: MODEL POTENTIAL +------------------------------ +Loading Hartree-Fock densities ... done +Calculating cut-offs ... done +Initializing the effective Hamiltonian ... done +Setting up the integral package (SHARK) ... done +Starting the Coulomb interaction ... done ( 0.0 sec) +Reading the grid ... done +Mapping shells ... done +Starting the XC term evaluation ... done ( 0.0 sec) +Transforming the Hamiltonian ... done ( 0.0 sec) +Diagonalizing the Hamiltonian ... done ( 0.0 sec) +Back transforming the eigenvectors ... done ( 0.0 sec) +Now organizing SCF variables ... done + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + + + ... the calculation is a CASSCF calculation -I'm leaving here GOOD LUCK!!! + + + + ************************************************************ + * Program running with 16 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA-CASSCF +------------------------------------------------------------------------------- + +Setting up the integral package ... done +Building the CAS space ... done (21 configurations for Mult=3) + +SYSTEM-SPECIFIC SETTINGS: +Number of active electrons ... 12 +Number of active orbitals ... 7 +Total number of electrons ... 16 +Total number of orbitals ... 92 + +Determined orbital ranges: + Internal 0 - 1 ( 2 orbitals) + Active 2 - 8 ( 7 orbitals) + External 9 - 91 ( 83 orbitals) +Number of rotation parameters ... 761 + +CI-STEP: +CI strategy ... General CI +Number of multiplicity blocks ... 1 +BLOCK 1 WEIGHT= 1.0000 + Multiplicity ... 3 + #(Configurations) ... 21 + #(CSFs) ... 21 + #(Roots) ... 1 + ROOT=0 WEIGHT= 1.000000 + + PrintLevel ... 1 + N(GuessMat) ... 512 + MaxDim(CI) ... 10 + MaxIter(CI) ... 64 + Energy Tolerance CI ... 2.50e-09 + Residual Tolerance CI ... 2.50e-09 + Shift(CI) ... 1.00e-04 + +INTEGRAL-TRANSFORMATION-STEP: + Algorithm ... EXACT + +ORBITAL-IMPROVEMENT-STEP: + Algorithm ... SuperCI(PT) + Default Parametrization ... CAYLEY + Act-Act rotations ... depends on algorithm used + + Note: SuperCI(PT) will ignore FreezeIE, FreezeAct and FreezeGrad. In general Default settings are encouraged. + In conjunction with ShiftUp, ShiftDn or GradScaling the performance of SuperCI(PT) is less optimal. + + MaxRot ... 2.00e-01 + Max. no of vectors (DIIS) ... 15 + DThresh (cut-off) metric ... 1.00e-06 + Switch step at gradient ... 3.00e-02 + Switch step at iteration ... 50 + Switch step to ... SuperCI(PT) + +SCF-SETTINGS: + Incremental ... on + RIJCOSX approximation ... off + RI-JK approximation ... off + AO integral handling ... DIRECT + Integral Neglect Thresh ... 2.50e-11 + Primitive cutoff TCut ... 2.50e-12 + Energy convergence tolerance ... 2.50e-08 + Orbital gradient convergence ... 2.50e-04 + Max. number of iterations ... 999 + + +FINAL ORBITALS: + Active Orbitals ... natural + Internal Orbitals ... canonical + External Orbitals ... canonical + +------------------ +CAS-SCF ITERATIONS +------------------ + + +MACRO-ITERATION 1: + --- Inactive Energy E0 = -102.50929621 Eh +CI-ITERATION 0: + -149.663088624 0.000000000000 ( 0.00) + CI-PROBLEM SOLVED + DENSITIES MADE + + <<<<<<<<<<<<<<<<<>>>>>>>>>>>>>>>>> + +BLOCK 1 MULT= 3 NROOTS= 1 +ROOT 0: E= -149.6630886244 Eh + 0.94326 [ 20]: 2222211 + 0.05674 [ 15]: 2221122 + + <<<<<<<<<<<<<<<<<>>>>>>>>>>>>>>>>> + + E(CAS)= -149.663088624 Eh DE= 0.000000e+00 + --- Energy gap subspaces: Ext-Act = 0.361 Act-Int = 19.051 + N(occ)= 2.00000 2.00000 2.00000 1.94326 1.94326 1.05674 1.05674 + ||g|| = 1.533852e+00 Max(G)= 6.797319e-01 Rot=91,1 + --- Orbital Update [SuperCI(PT)] + --- Canonicalize Internal Space + --- Canonicalize External Space + --- SX_PT (Skipped TA=0 IT=3): ||X|| = 0.068163115 Max(X)(15,7) = 0.026169488 + --- SFit(Active Orbitals) + +MACRO-ITERATION 2: + --- Inactive Energy E0 = -102.52804583 Eh +CI-ITERATION 0: + -149.691215391 0.000000000000 ( 0.00) + CI-PROBLEM SOLVED + DENSITIES MADE + E(CAS)= -149.691215391 Eh DE= -2.812677e-02 + --- Energy gap subspaces: Ext-Act = 0.355 Act-Int = 19.083 + N(occ)= 2.00000 2.00000 2.00000 1.94373 1.94373 1.05627 1.05627 + ||g|| = 1.249785e-01 Max(G)= 4.500059e-02 Rot=91,1 + --- Orbital Update [SuperCI(PT)] + --- Canonicalize Internal Space + --- Canonicalize External Space + --- SX_PT (Skipped TA=0 IT=3): ||X|| = 0.014201765 Max(X)(14,7) = -0.005469492 + --- SFit(Active Orbitals) + +MACRO-ITERATION 3: + --- Inactive Energy E0 = -102.52861899 Eh +CI-ITERATION 0: + -149.691706573 0.000000000000 ( 0.00) + CI-PROBLEM SOLVED + DENSITIES MADE + E(CAS)= -149.691706573 Eh DE= -4.911812e-04 + --- Energy gap subspaces: Ext-Act = 0.353 Act-Int = 19.078 + N(occ)= 2.00000 2.00000 2.00000 1.94377 1.94377 1.05623 1.05623 + ||g|| = 1.935374e-02 Max(G)= -6.069395e-03 Rot=62,4 + --- Orbital Update [SuperCI(PT)] + --- Canonicalize Internal Space + --- Canonicalize External Space + --- SX_PT (Skipped TA=0 IT=3): ||X|| = 0.002780538 Max(X)(14,8) = 0.001179328 + --- SFit(Active Orbitals) + +MACRO-ITERATION 4: + --- Inactive Energy E0 = -102.52864127 Eh +CI-ITERATION 0: + -149.691723077 0.000000000000 ( 0.00) + CI-PROBLEM SOLVED + DENSITIES MADE + E(CAS)= -149.691723077 Eh DE= -1.650475e-05 + --- Energy gap subspaces: Ext-Act = 0.352 Act-Int = 19.079 + N(occ)= 2.00000 2.00000 2.00000 1.94379 1.94379 1.05621 1.05621 + ||g|| = 3.207605e-03 Max(G)= -1.034912e-03 Rot=90,0 + --- Orbital Update [SuperCI(PT)] + --- Canonicalize Internal Space + --- Canonicalize External Space + --- SX_PT (Skipped TA=0 IT=3): ||X|| = 0.000317454 Max(X)(14,7) = -0.000114234 + --- SFit(Active Orbitals) + +MACRO-ITERATION 5: + --- Inactive Energy E0 = -102.52862061 Eh +CI-ITERATION 0: + -149.691723423 0.000000000000 ( 0.00) + CI-PROBLEM SOLVED + DENSITIES MADE + E(CAS)= -149.691723423 Eh DE= -3.454465e-07 + --- Energy gap subspaces: Ext-Act = 0.352 Act-Int = 19.079 + N(occ)= 2.00000 2.00000 2.00000 1.94380 1.94380 1.05620 1.05620 + ||g|| = 3.448241e-04 Max(G)= 1.172317e-04 Rot=91,1 + --- Orbital Update [SuperCI(PT)] + --- Canonicalize Internal Space + --- Canonicalize External Space + --- SX_PT (Skipped TA=0 IT=3): ||X|| = 0.000038797 Max(X)(25,8) = 0.000013309 + --- SFit(Active Orbitals) + +MACRO-ITERATION 6: + --- Inactive Energy E0 = -102.52862262 Eh +CI-ITERATION 0: + -149.691723428 0.000000000000 ( 0.00) + CI-PROBLEM SOLVED + DENSITIES MADE + E(CAS)= -149.691723428 Eh DE= -5.171614e-09 + --- Energy gap subspaces: Ext-Act = 0.352 Act-Int = 19.079 + N(occ)= 2.00000 2.00000 2.00000 1.94379 1.94379 1.05621 1.05621 + ||g|| = 5.912935e-05 Max(G)= -1.663872e-05 Rot=30,4 + ---- THE CAS-SCF ENERGY HAS CONVERGED ---- + ---- THE CAS-SCF GRADIENT HAS CONVERGED ---- + --- FINALIZING ORBITALS --- + ---- DOING ONE FINAL ITERATION FOR PRINTING ---- + --- Forming Natural Orbitals + --- Canonicalize Internal Space + --- Canonicalize External Space + +MACRO-ITERATION 7: + --- Inactive Energy E0 = -102.52862262 Eh + --- All densities will be recomputed +CI-ITERATION 0: + -149.691723428 0.000000000000 ( 0.00) + CI-PROBLEM SOLVED + DENSITIES MADE + E(CAS)= -149.691723428 Eh DE= -5.184120e-11 + --- Energy gap subspaces: Ext-Act = 0.321 Act-Int = 19.112 + N(occ)= 2.00000 2.00000 2.00000 1.94379 1.94379 1.05621 1.05621 + ||g|| = 5.912952e-05 Max(G)= -1.814644e-05 Rot=30,3 +-------------- +CASSCF RESULTS +-------------- + +Final CASSCF energy : -149.691723428 Eh -4073.3189 eV + +---------------- +ORBITAL ENERGIES +---------------- + + NO OCC E(Eh) E(eV) + 0 2.0000 -20.717072 -563.7402 + 1 2.0000 -20.716076 -563.7131 + 2 2.0000 -1.103010 -30.0144 + 3 2.0000 -0.754136 -20.5211 + 4 2.0000 -1.603873 -43.6436 + 5 1.9438 -0.687927 -18.7194 + 6 1.9438 -0.687927 -18.7194 + 7 1.0562 -0.220276 -5.9940 + 8 1.0562 -0.220276 -5.9940 + 9 0.0000 0.100407 2.7322 + 10 0.0000 0.144727 3.9382 + 11 0.0000 0.154666 4.2087 + 12 0.0000 0.154666 4.2087 + 13 0.0000 0.202570 5.5122 + 14 0.0000 0.202570 5.5122 + 15 0.0000 0.204106 5.5540 + 16 0.0000 0.328917 8.9503 + 17 0.0000 0.503914 13.7122 + 18 0.0000 0.572608 15.5815 + 19 0.0000 0.572608 15.5815 + 20 0.0000 0.672009 18.2863 + 21 0.0000 0.759907 20.6781 + 22 0.0000 0.759907 20.6781 + 23 0.0000 0.799552 21.7569 + 24 0.0000 0.799552 21.7569 + 25 0.0000 0.819143 22.2900 + 26 0.0000 0.819143 22.2900 + 27 0.0000 0.858834 23.3701 + 28 0.0000 0.905770 24.6473 + 29 0.0000 0.905770 24.6473 + 30 0.0000 0.981290 26.7022 + 31 0.0000 1.000087 27.2137 + 32 0.0000 1.158714 31.5302 + 33 0.0000 1.158714 31.5302 + 34 0.0000 1.563802 42.5532 + 35 0.0000 1.859277 50.5935 + 36 0.0000 1.859277 50.5935 + 37 0.0000 1.870556 50.9004 + 38 0.0000 1.870556 50.9004 + 39 0.0000 1.921335 52.2822 + 40 0.0000 1.921335 52.2822 + 41 0.0000 2.190962 59.6191 + 42 0.0000 2.190962 59.6191 + 43 0.0000 2.194096 59.7044 + 44 0.0000 2.210971 60.1636 + 45 0.0000 2.210971 60.1636 + 46 0.0000 2.256256 61.3959 + 47 0.0000 2.256256 61.3959 + 48 0.0000 2.319170 63.1078 + 49 0.0000 2.319170 63.1078 + 50 0.0000 2.352583 64.0170 + 51 0.0000 2.686961 73.1159 + 52 0.0000 2.686961 73.1159 + 53 0.0000 2.688094 73.1468 + 54 0.0000 2.832791 77.0842 + 55 0.0000 2.832791 77.0842 + 56 0.0000 2.884187 78.4827 + 57 0.0000 3.116695 84.8096 + 58 0.0000 3.116695 84.8096 + 59 0.0000 3.513940 95.6192 + 60 0.0000 4.122064 112.1671 + 61 0.0000 4.122064 112.1671 + 62 0.0000 4.389435 119.4426 + 63 0.0000 4.928176 134.1025 + 64 0.0000 4.928176 134.1025 + 65 0.0000 5.945711 161.7910 + 66 0.0000 5.945711 161.7910 + 67 0.0000 6.014172 163.6539 + 68 0.0000 6.097579 165.9236 + 69 0.0000 6.097579 165.9236 + 70 0.0000 6.202505 168.7787 + 71 0.0000 6.319948 171.9745 + 72 0.0000 6.319948 171.9745 + 73 0.0000 6.506812 177.0594 + 74 0.0000 6.506812 177.0594 + 75 0.0000 6.862856 186.7478 + 76 0.0000 6.896937 187.6752 + 77 0.0000 6.896937 187.6752 + 78 0.0000 6.930970 188.6013 + 79 0.0000 6.930970 188.6013 + 80 0.0000 7.050934 191.8657 + 81 0.0000 7.050934 191.8657 + 82 0.0000 7.186381 195.5514 + 83 0.0000 7.186381 195.5514 + 84 0.0000 7.473447 203.3628 + 85 0.0000 7.473447 203.3628 + 86 0.0000 7.751428 210.9271 + 87 0.0000 7.751428 210.9271 + 88 0.0000 7.962231 216.6633 + 89 0.0000 8.289863 225.5786 + 90 0.0000 12.576760 342.2310 + 91 0.0000 14.215041 386.8109 + + +--------------------------------------------- +CAS-SCF STATES FOR BLOCK 1 MULT= 3 NROOTS= 1 +--------------------------------------------- + +ROOT 0: E= -149.6917234280 Eh + 0.94379 [ 20]: 2222211 + 0.05621 [ 15]: 2221122 + + +-------------- +DENSITY MATRIX +-------------- + + 0 1 2 3 4 5 + 0 2.000000 -0.000000 -0.000000 0.000000 -0.000000 0.000000 + 1 -0.000000 2.000000 -0.000000 0.000000 -0.000000 0.000000 + 2 -0.000000 -0.000000 2.000000 -0.000000 0.000000 0.000000 + 3 0.000000 0.000000 -0.000000 1.943795 0.000000 -0.000000 + 4 -0.000000 -0.000000 0.000000 0.000000 1.943795 -0.000000 + 5 0.000000 0.000000 0.000000 -0.000000 -0.000000 1.056205 + 6 -0.000000 -0.000000 0.000000 -0.000000 0.000000 -0.000000 + 6 + 0 -0.000000 + 1 -0.000000 + 2 0.000000 + 3 -0.000000 + 4 0.000000 + 5 -0.000000 + 6 1.056205 +Trace of the electron density: 12.000000 +Extracting Spin-Density from 2-RDM (MULT=3) ... done + +------------------- +SPIN-DENSITY MATRIX +------------------- + + 0 1 2 3 4 5 + 0 0.000000 0.000000 0.000000 -0.000000 0.000000 -0.000000 + 1 0.000000 0.000000 0.000000 -0.000000 0.000000 -0.000000 + 2 0.000000 0.000000 0.000000 0.000000 -0.000000 -0.000000 + 3 -0.000000 -0.000000 0.000000 0.056205 -0.000000 0.000000 + 4 0.000000 0.000000 -0.000000 -0.000000 0.056205 0.000000 + 5 -0.000000 -0.000000 -0.000000 0.000000 0.000000 0.943795 + 6 0.000000 0.000000 -0.000000 0.000000 -0.000000 0.000000 + 6 + 0 0.000000 + 1 0.000000 + 2 -0.000000 + 3 0.000000 + 4 -0.000000 + 5 0.000000 + 6 0.943795 +Trace of the spin density: 2.000000 + +----------------- +ENERGY COMPONENTS +----------------- + +One electron energy : -261.360867394 Eh -7111.9908 eV +Two electron energy : 83.801853262 Eh 2280.3644 eV +Nuclear repulsion energy : 27.867290704 Eh 758.3075 eV + ---------------- + -149.691723428 + +Kinetic energy : 149.489892464 Eh 4067.8268 eV +Potential energy : -299.181615892 Eh -8141.1457 eV +Virial ratio : -2.001350131 + ---------------- + -149.691723428 + +Core energy : -102.528622621 Eh -2789.9457 eV + + +---------------------------- +LOEWDIN ORBITAL-COMPOSITIONS +---------------------------- + + 0 1 2 3 4 5 + -20.71707 -20.71608 -1.10301 -0.75414 -1.60387 -0.68793 + 2.00000 2.00000 2.00000 2.00000 2.00000 1.94379 + -------- -------- -------- -------- -------- -------- + 0 O s 49.0 49.1 20.9 7.4 45.9 0.0 + 0 O pz 0.3 0.2 30.1 27.8 7.4 0.0 + 0 O px 0.0 0.0 0.0 0.0 0.0 3.4 + 0 O py 0.0 0.0 0.0 0.0 0.0 42.7 + 0 O dz2 0.4 0.3 4.4 2.5 1.7 0.0 + 0 O dxz 0.0 0.0 0.0 0.0 0.0 0.2 + 0 O dyz 0.0 0.0 0.0 0.0 0.0 2.2 + 0 O f0 0.3 0.4 1.2 0.4 0.4 0.0 + 0 O f+1 0.0 0.0 0.0 0.0 0.0 0.1 + 0 O f-1 0.0 0.0 0.0 0.0 0.0 1.4 + 1 O s 49.0 49.1 35.2 19.7 19.4 0.0 + 1 O pz 0.3 0.2 4.7 40.9 19.7 0.0 + 1 O px 0.0 0.0 0.0 0.0 0.0 3.4 + 1 O py 0.0 0.0 0.0 0.0 0.0 42.7 + 1 O dz2 0.4 0.3 2.8 1.2 4.5 0.0 + 1 O dxz 0.0 0.0 0.0 0.0 0.0 0.2 + 1 O dyz 0.0 0.0 0.0 0.0 0.0 2.2 + 1 O f0 0.3 0.4 0.7 0.1 1.2 0.0 + 1 O f+1 0.0 0.0 0.0 0.0 0.0 0.1 + 1 O f-1 0.0 0.0 0.0 0.0 0.0 1.4 + + 6 7 8 9 10 11 + -0.68793 -0.22028 -0.22028 0.10041 0.14473 0.15467 + 1.94379 1.05621 1.05621 0.00000 0.00000 0.00000 + -------- -------- -------- -------- -------- -------- + 0 O s 0.0 0.0 0.0 1.6 38.8 0.0 + 0 O pz 0.0 0.0 0.0 47.4 10.8 0.0 + 0 O px 42.7 0.0 40.0 0.0 0.0 20.3 + 0 O py 3.4 40.0 0.0 0.0 0.0 29.3 + 0 O dz2 0.0 0.0 0.0 1.0 0.2 0.0 + 0 O dxz 2.2 0.0 7.0 0.0 0.0 0.1 + 0 O dyz 0.2 7.0 0.0 0.0 0.0 0.1 + 0 O f0 0.0 0.0 0.0 0.0 0.2 0.0 + 0 O f+1 1.4 0.0 3.0 0.0 0.0 0.1 + 0 O f-1 0.1 3.0 0.0 0.0 0.0 0.1 + 1 O s 0.0 0.0 0.0 1.6 38.8 0.0 + 1 O pz 0.0 0.0 0.0 47.4 10.8 0.0 + 1 O px 42.7 0.0 40.0 0.0 0.0 20.3 + 1 O py 3.4 40.0 0.0 0.0 0.0 29.3 + 1 O dz2 0.0 0.0 0.0 1.0 0.2 0.0 + 1 O dxz 2.2 0.0 7.0 0.0 0.0 0.1 + 1 O dyz 0.2 7.0 0.0 0.0 0.0 0.1 + 1 O f0 0.0 0.0 0.0 0.0 0.2 0.0 + 1 O f+1 1.4 0.0 3.0 0.0 0.0 0.1 + 1 O f-1 0.1 3.0 0.0 0.0 0.0 0.1 + + 12 13 14 15 16 17 + 0.15467 0.20257 0.20257 0.20411 0.32892 0.50391 + 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 + -------- -------- -------- -------- -------- -------- + 0 O s 0.0 0.0 0.0 8.0 38.7 6.0 + 0 O pz 0.0 0.0 0.0 35.6 8.9 23.6 + 0 O px 29.3 20.6 26.1 0.0 0.0 0.0 + 0 O py 20.3 26.1 20.6 0.0 0.0 0.0 + 0 O dz2 0.0 0.0 0.0 6.3 1.7 19.9 + 0 O dxz 0.1 1.4 1.8 0.0 0.0 0.0 + 0 O dyz 0.1 1.8 1.4 0.0 0.0 0.0 + 0 O f0 0.0 0.0 0.0 0.2 0.7 0.4 + 0 O f+1 0.1 0.0 0.1 0.0 0.0 0.0 + 1 O s 0.0 0.0 0.0 8.0 38.7 6.0 + 1 O pz 0.0 0.0 0.0 35.6 8.9 23.6 + 1 O px 29.3 20.6 26.1 0.0 0.0 0.0 + 1 O py 20.3 26.1 20.6 0.0 0.0 0.0 + 1 O dz2 0.0 0.0 0.0 6.3 1.7 19.9 + 1 O dxz 0.1 1.4 1.8 0.0 0.0 0.0 + 1 O dyz 0.1 1.8 1.4 0.0 0.0 0.0 + 1 O f0 0.0 0.0 0.0 0.2 0.7 0.4 + 1 O f+1 0.1 0.0 0.1 0.0 0.0 0.0 + + 18 19 20 21 22 23 + 0.57261 0.57261 0.67201 0.75991 0.75991 0.79955 + 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 + -------- -------- -------- -------- -------- -------- + 0 O s 0.0 0.0 11.1 0.0 0.0 0.0 + 0 O pz 0.0 0.0 10.3 0.0 0.0 0.0 + 0 O px 0.0 0.0 0.0 4.5 5.6 0.0 + 0 O py 0.0 0.0 0.0 5.6 4.5 0.0 + 0 O dz2 0.0 0.0 28.4 0.0 0.0 0.0 + 0 O dxz 0.0 0.0 0.0 17.5 21.6 0.0 + 0 O dyz 0.0 0.0 0.0 21.6 17.5 0.0 + 0 O dx2y2 0.0 49.7 0.0 0.0 0.0 0.0 + 0 O dxy 49.7 0.0 0.0 0.0 0.0 46.1 + 0 O f0 0.0 0.0 0.2 0.0 0.0 0.0 + 0 O f+1 0.0 0.0 0.0 0.3 0.4 0.0 + 0 O f-1 0.0 0.0 0.0 0.4 0.3 0.0 + 0 O f+2 0.0 0.3 0.0 0.0 0.0 0.0 + 0 O f-2 0.3 0.0 0.0 0.0 0.0 3.9 + 1 O s 0.0 0.0 11.1 0.0 0.0 0.0 + 1 O pz 0.0 0.0 10.3 0.0 0.0 0.0 + 1 O px 0.0 0.0 0.0 4.5 5.6 0.0 + 1 O py 0.0 0.0 0.0 5.6 4.5 0.0 + 1 O dz2 0.0 0.0 28.4 0.0 0.0 0.0 + 1 O dxz 0.0 0.0 0.0 17.5 21.6 0.0 + 1 O dyz 0.0 0.0 0.0 21.6 17.5 0.0 + 1 O dx2y2 0.0 49.7 0.0 0.0 0.0 0.0 + 1 O dxy 49.7 0.0 0.0 0.0 0.0 46.1 + 1 O f0 0.0 0.0 0.2 0.0 0.0 0.0 + 1 O f+1 0.0 0.0 0.0 0.3 0.4 0.0 + 1 O f-1 0.0 0.0 0.0 0.4 0.3 0.0 + 1 O f+2 0.0 0.3 0.0 0.0 0.0 0.0 + 1 O f-2 0.3 0.0 0.0 0.0 0.0 3.9 + + 24 25 26 27 28 29 + 0.79955 0.81914 0.81914 0.85883 0.90577 0.90577 + 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 + -------- -------- -------- -------- -------- -------- + 0 O s 0.0 0.0 0.0 10.0 0.0 0.0 + 0 O pz 0.0 0.0 0.0 4.4 0.0 0.0 + 0 O px 0.0 9.3 0.0 0.0 19.3 20.7 + 0 O py 0.0 0.0 9.3 0.0 20.7 19.3 + 0 O dz2 0.0 0.0 0.0 30.1 0.0 0.0 + 0 O dxz 0.0 36.9 0.0 0.0 3.8 4.1 + 0 O dyz 0.0 0.0 36.9 0.0 4.1 3.8 + 0 O dx2y2 46.1 0.0 0.0 0.0 0.0 0.0 + 0 O f0 0.0 0.0 0.0 5.5 0.0 0.0 + 0 O f+1 0.0 3.8 0.0 0.0 1.0 1.1 + 0 O f-1 0.0 0.0 3.8 0.0 1.1 1.0 + 0 O f+2 3.9 0.0 0.0 0.0 0.0 0.0 + 1 O s 0.0 0.0 0.0 10.0 0.0 0.0 + 1 O pz 0.0 0.0 0.0 4.4 0.0 0.0 + 1 O px 0.0 9.3 0.0 0.0 19.3 20.7 + 1 O py 0.0 0.0 9.3 0.0 20.7 19.3 + 1 O dz2 0.0 0.0 0.0 30.1 0.0 0.0 + 1 O dxz 0.0 36.9 0.0 0.0 3.8 4.1 + 1 O dyz 0.0 0.0 36.9 0.0 4.1 3.8 + 1 O dx2y2 46.1 0.0 0.0 0.0 0.0 0.0 + 1 O f0 0.0 0.0 0.0 5.5 0.0 0.0 + 1 O f+1 0.0 3.8 0.0 0.0 1.0 1.1 + 1 O f-1 0.0 0.0 3.8 0.0 1.1 1.0 + 1 O f+2 3.9 0.0 0.0 0.0 0.0 0.0 + + 30 31 32 33 34 35 + 0.98129 1.00009 1.15871 1.15871 1.56380 1.85928 + 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 + -------- -------- -------- -------- -------- -------- + 0 O s 27.3 7.5 0.0 0.0 3.5 0.0 + 0 O pz 22.5 40.0 0.0 0.0 5.9 0.0 + 0 O px 0.0 0.0 37.7 0.5 0.0 0.0 + 0 O py 0.0 0.0 0.5 37.7 0.0 0.0 + 0 O dz2 0.2 2.3 0.0 0.0 12.2 0.0 + 0 O dxz 0.0 0.0 1.7 0.0 0.0 0.0 + 0 O dyz 0.0 0.0 0.0 1.7 0.0 0.0 + 0 O dxy 0.0 0.0 0.0 0.0 0.0 29.8 + 0 O f0 0.0 0.2 0.0 0.0 28.4 0.0 + 0 O f+1 0.0 0.0 9.9 0.1 0.0 0.0 + 0 O f-1 0.0 0.0 0.1 9.9 0.0 0.0 + 0 O f-2 0.0 0.0 0.0 0.0 0.0 20.2 + 1 O s 27.3 7.5 0.0 0.0 3.5 0.0 + 1 O pz 22.5 40.0 0.0 0.0 5.9 0.0 + 1 O px 0.0 0.0 37.7 0.5 0.0 0.0 + 1 O py 0.0 0.0 0.5 37.7 0.0 0.0 + 1 O dz2 0.2 2.3 0.0 0.0 12.2 0.0 + 1 O dxz 0.0 0.0 1.7 0.0 0.0 0.0 + 1 O dyz 0.0 0.0 0.0 1.7 0.0 0.0 + 1 O dxy 0.0 0.0 0.0 0.0 0.0 29.8 + 1 O f0 0.0 0.2 0.0 0.0 28.4 0.0 + 1 O f+1 0.0 0.0 9.9 0.1 0.0 0.0 + 1 O f-1 0.0 0.0 0.1 9.9 0.0 0.0 + 1 O f-2 0.0 0.0 0.0 0.0 0.0 20.2 + + 36 37 38 39 40 41 + 1.85928 1.87056 1.87056 1.92133 1.92133 2.19096 + 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 + -------- -------- -------- -------- -------- -------- + 0 O px 0.0 0.0 0.0 0.7 0.6 0.0 + 0 O py 0.0 0.0 0.0 0.6 0.7 0.0 + 0 O dxz 0.0 0.0 0.0 24.8 22.8 0.0 + 0 O dyz 0.0 0.0 0.0 22.8 24.8 0.0 + 0 O dx2y2 29.8 0.0 0.0 0.0 0.0 0.0 + 0 O dxy 0.0 0.0 0.0 0.0 0.0 39.2 + 0 O f+1 0.0 0.0 0.0 0.6 0.5 0.0 + 0 O f-1 0.0 0.0 0.0 0.5 0.6 0.0 + 0 O f+2 20.2 0.0 0.0 0.0 0.0 0.0 + 0 O f-2 0.0 0.0 0.0 0.0 0.0 10.8 + 0 O f+3 0.0 2.9 47.1 0.0 0.0 0.0 + 0 O f-3 0.0 47.1 2.9 0.0 0.0 0.0 + 1 O px 0.0 0.0 0.0 0.7 0.6 0.0 + 1 O py 0.0 0.0 0.0 0.6 0.7 0.0 + 1 O dxz 0.0 0.0 0.0 24.8 22.8 0.0 + 1 O dyz 0.0 0.0 0.0 22.8 24.8 0.0 + 1 O dx2y2 29.8 0.0 0.0 0.0 0.0 0.0 + 1 O dxy 0.0 0.0 0.0 0.0 0.0 39.2 + 1 O f+1 0.0 0.0 0.0 0.6 0.5 0.0 + 1 O f-1 0.0 0.0 0.0 0.5 0.6 0.0 + 1 O f+2 20.2 0.0 0.0 0.0 0.0 0.0 + 1 O f-2 0.0 0.0 0.0 0.0 0.0 10.8 + 1 O f+3 0.0 2.9 47.1 0.0 0.0 0.0 + 1 O f-3 0.0 47.1 2.9 0.0 0.0 0.0 + + 42 43 44 45 46 47 + 2.19096 2.19410 2.21097 2.21097 2.25626 2.25626 + 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 + -------- -------- -------- -------- -------- -------- + 0 O s 0.0 0.6 0.0 0.0 0.0 0.0 + 0 O pz 0.0 1.2 0.0 0.0 0.0 0.0 + 0 O dz2 0.0 36.9 0.0 0.0 0.0 0.0 + 0 O dx2y2 39.2 0.0 0.0 20.5 0.0 0.0 + 0 O dxy 0.0 0.0 20.5 0.0 0.0 0.0 + 0 O f0 0.0 11.3 0.0 0.0 0.0 0.0 + 0 O f+2 10.8 0.0 0.0 29.5 0.0 0.0 + 0 O f-2 0.0 0.0 29.5 0.0 0.0 0.0 + 0 O f+3 0.0 0.0 0.0 0.0 5.1 44.9 + 0 O f-3 0.0 0.0 0.0 0.0 44.9 5.1 + 1 O s 0.0 0.6 0.0 0.0 0.0 0.0 + 1 O pz 0.0 1.2 0.0 0.0 0.0 0.0 + 1 O dz2 0.0 36.9 0.0 0.0 0.0 0.0 + 1 O dx2y2 39.2 0.0 0.0 20.5 0.0 0.0 + 1 O dxy 0.0 0.0 20.5 0.0 0.0 0.0 + 1 O f0 0.0 11.3 0.0 0.0 0.0 0.0 + 1 O f+2 10.8 0.0 0.0 29.5 0.0 0.0 + 1 O f-2 0.0 0.0 29.5 0.0 0.0 0.0 + 1 O f+3 0.0 0.0 0.0 0.0 5.1 44.9 + 1 O f-3 0.0 0.0 0.0 0.0 44.9 5.1 + + 48 49 50 51 52 53 + 2.31917 2.31917 2.35258 2.68696 2.68696 2.68809 + 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 + -------- -------- -------- -------- -------- -------- + 0 O s 0.0 0.0 14.3 0.0 0.0 22.0 + 0 O pz 0.0 0.0 1.5 0.0 0.0 16.2 + 0 O px 4.7 0.0 0.0 2.1 0.8 0.0 + 0 O py 0.0 4.7 0.0 0.8 2.1 0.0 + 0 O dz2 0.0 0.0 19.9 0.0 0.0 8.5 + 0 O dxz 18.2 0.1 0.0 2.0 0.8 0.0 + 0 O dyz 0.1 18.2 0.0 0.8 2.0 0.0 + 0 O f0 0.0 0.0 14.2 0.0 0.0 3.3 + 0 O f+1 26.8 0.1 0.0 31.7 12.6 0.0 + 0 O f-1 0.1 26.8 0.0 12.6 31.7 0.0 + 1 O s 0.0 0.0 14.3 0.0 0.0 22.0 + 1 O pz 0.0 0.0 1.5 0.0 0.0 16.2 + 1 O px 4.7 0.0 0.0 2.1 0.8 0.0 + 1 O py 0.0 4.7 0.0 0.8 2.1 0.0 + 1 O dz2 0.0 0.0 19.9 0.0 0.0 8.5 + 1 O dxz 18.2 0.1 0.0 2.0 0.8 0.0 + 1 O dyz 0.1 18.2 0.0 0.8 2.0 0.0 + 1 O f0 0.0 0.0 14.2 0.0 0.0 3.3 + 1 O f+1 26.8 0.1 0.0 31.7 12.6 0.0 + 1 O f-1 0.1 26.8 0.0 12.6 31.7 0.0 + + 54 55 56 57 58 59 + 2.83279 2.83279 2.88419 3.11670 3.11670 3.51394 + 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 + -------- -------- -------- -------- -------- -------- + 0 O s 0.0 0.0 9.7 0.0 0.0 17.6 + 0 O pz 0.0 0.0 5.1 0.0 0.0 16.4 + 0 O px 0.0 0.0 0.0 17.7 0.2 0.0 + 0 O py 0.0 0.0 0.0 0.2 17.7 0.0 + 0 O dz2 0.0 0.0 9.8 0.0 0.0 9.8 + 0 O dxz 0.0 0.0 0.0 24.9 0.3 0.0 + 0 O dyz 0.0 0.0 0.0 0.3 24.9 0.0 + 0 O dx2y2 0.0 14.5 0.0 0.0 0.0 0.0 + 0 O dxy 14.5 0.0 0.0 0.0 0.0 0.0 + 0 O f0 0.0 0.0 25.4 0.0 0.0 6.1 + 0 O f+1 0.0 0.0 0.0 6.8 0.1 0.0 + 0 O f-1 0.0 0.0 0.0 0.1 6.8 0.0 + 0 O f+2 0.0 35.5 0.0 0.0 0.0 0.0 + 0 O f-2 35.5 0.0 0.0 0.0 0.0 0.0 + 1 O s 0.0 0.0 9.7 0.0 0.0 17.6 + 1 O pz 0.0 0.0 5.1 0.0 0.0 16.4 + 1 O px 0.0 0.0 0.0 17.7 0.2 0.0 + 1 O py 0.0 0.0 0.0 0.2 17.7 0.0 + 1 O dz2 0.0 0.0 9.8 0.0 0.0 9.8 + 1 O dxz 0.0 0.0 0.0 24.9 0.3 0.0 + 1 O dyz 0.0 0.0 0.0 0.3 24.9 0.0 + 1 O dx2y2 0.0 14.5 0.0 0.0 0.0 0.0 + 1 O dxy 14.5 0.0 0.0 0.0 0.0 0.0 + 1 O f0 0.0 0.0 25.4 0.0 0.0 6.1 + 1 O f+1 0.0 0.0 0.0 6.8 0.1 0.0 + 1 O f-1 0.0 0.0 0.0 0.1 6.8 0.0 + 1 O f+2 0.0 35.5 0.0 0.0 0.0 0.0 + 1 O f-2 35.5 0.0 0.0 0.0 0.0 0.0 + + 60 61 62 63 64 65 + 4.12206 4.12206 4.38944 4.92818 4.92818 5.94571 + 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 + -------- -------- -------- -------- -------- -------- + 0 O s 0.0 0.0 2.3 0.0 0.0 0.0 + 0 O pz 0.0 0.0 41.4 0.0 0.0 0.0 + 0 O px 24.6 25.1 0.0 37.8 0.0 0.1 + 0 O py 25.1 24.6 0.0 0.0 37.8 0.1 + 0 O dz2 0.0 0.0 3.9 0.0 0.0 0.0 + 0 O dxz 0.1 0.1 0.0 9.3 0.0 1.8 + 0 O dyz 0.1 0.1 0.0 0.0 9.3 1.8 + 0 O f0 0.0 0.0 2.5 0.0 0.0 0.0 + 0 O f+1 0.1 0.1 0.0 2.8 0.0 23.4 + 0 O f-1 0.1 0.1 0.0 0.0 2.8 22.8 + 1 O s 0.0 0.0 2.3 0.0 0.0 0.0 + 1 O pz 0.0 0.0 41.4 0.0 0.0 0.0 + 1 O px 24.6 25.1 0.0 37.8 0.0 0.1 + 1 O py 25.1 24.6 0.0 0.0 37.8 0.1 + 1 O dz2 0.0 0.0 3.9 0.0 0.0 0.0 + 1 O dxz 0.1 0.1 0.0 9.3 0.0 1.8 + 1 O dyz 0.1 0.1 0.0 0.0 9.3 1.8 + 1 O f0 0.0 0.0 2.5 0.0 0.0 0.0 + 1 O f+1 0.1 0.1 0.0 2.8 0.0 23.4 + 1 O f-1 0.1 0.1 0.0 0.0 2.8 22.8 + + 66 67 68 69 70 71 + 5.94571 6.01417 6.09758 6.09758 6.20251 6.31995 + 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 + -------- -------- -------- -------- -------- -------- + 0 O s 0.0 2.2 0.0 0.0 2.8 0.0 + 0 O pz 0.0 0.3 0.0 0.0 9.6 0.0 + 0 O px 0.1 0.0 0.0 0.0 0.0 0.0 + 0 O py 0.1 0.0 0.0 0.0 0.0 0.0 + 0 O dz2 0.0 9.7 0.0 0.0 9.2 0.0 + 0 O dxz 1.8 0.0 0.0 0.0 0.0 0.0 + 0 O dyz 1.8 0.0 0.0 0.0 0.0 0.0 + 0 O dx2y2 0.0 0.0 0.2 0.0 0.0 0.0 + 0 O dxy 0.0 0.0 0.0 0.2 0.0 0.0 + 0 O f0 0.0 37.8 0.0 0.0 28.4 0.0 + 0 O f+1 22.8 0.0 0.0 0.0 0.0 0.0 + 0 O f-1 23.4 0.0 0.0 0.0 0.0 0.0 + 0 O f+2 0.0 0.0 49.8 0.0 0.0 0.0 + 0 O f-2 0.0 0.0 0.0 49.8 0.0 0.0 + 0 O f+3 0.0 0.0 0.0 0.0 0.0 48.5 + 0 O f-3 0.0 0.0 0.0 0.0 0.0 1.5 + 1 O s 0.0 2.2 0.0 0.0 2.8 0.0 + 1 O pz 0.0 0.3 0.0 0.0 9.6 0.0 + 1 O px 0.1 0.0 0.0 0.0 0.0 0.0 + 1 O py 0.1 0.0 0.0 0.0 0.0 0.0 + 1 O dz2 0.0 9.7 0.0 0.0 9.2 0.0 + 1 O dxz 1.8 0.0 0.0 0.0 0.0 0.0 + 1 O dyz 1.8 0.0 0.0 0.0 0.0 0.0 + 1 O dx2y2 0.0 0.0 0.2 0.0 0.0 0.0 + 1 O dxy 0.0 0.0 0.0 0.2 0.0 0.0 + 1 O f0 0.0 37.8 0.0 0.0 28.4 0.0 + 1 O f+1 22.8 0.0 0.0 0.0 0.0 0.0 + 1 O f-1 23.4 0.0 0.0 0.0 0.0 0.0 + 1 O f+2 0.0 0.0 49.8 0.0 0.0 0.0 + 1 O f-2 0.0 0.0 0.0 49.8 0.0 0.0 + 1 O f+3 0.0 0.0 0.0 0.0 0.0 48.5 + 1 O f-3 0.0 0.0 0.0 0.0 0.0 1.5 + + 72 73 74 75 76 77 + 6.31995 6.50681 6.50681 6.86286 6.89694 6.89694 + 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 + -------- -------- -------- -------- -------- -------- + 0 O s 0.0 0.0 0.0 8.4 0.0 0.0 + 0 O pz 0.0 0.0 0.0 14.1 0.0 0.0 + 0 O dz2 0.0 0.0 0.0 27.5 0.0 0.0 + 0 O dx2y2 0.0 0.0 0.0 0.0 49.9 0.0 + 0 O dxy 0.0 0.0 0.0 0.0 0.0 49.9 + 0 O f+2 0.0 0.0 0.0 0.0 0.1 0.0 + 0 O f-2 0.0 0.0 0.0 0.0 0.0 0.1 + 0 O f+3 1.5 0.1 49.9 0.0 0.0 0.0 + 0 O f-3 48.5 49.9 0.1 0.0 0.0 0.0 + 1 O s 0.0 0.0 0.0 8.4 0.0 0.0 + 1 O pz 0.0 0.0 0.0 14.1 0.0 0.0 + 1 O dz2 0.0 0.0 0.0 27.5 0.0 0.0 + 1 O dx2y2 0.0 0.0 0.0 0.0 49.9 0.0 + 1 O dxy 0.0 0.0 0.0 0.0 0.0 49.9 + 1 O f+2 0.0 0.0 0.0 0.0 0.1 0.0 + 1 O f-2 0.0 0.0 0.0 0.0 0.0 0.1 + 1 O f+3 1.5 0.1 49.9 0.0 0.0 0.0 + 1 O f-3 48.5 49.9 0.1 0.0 0.0 0.0 + + 78 79 80 81 82 83 + 6.93097 6.93097 7.05093 7.05093 7.18638 7.18638 + 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 + -------- -------- -------- -------- -------- -------- + 0 O dxz 0.0 0.0 0.0 0.0 25.0 21.2 + 0 O dyz 0.0 0.0 0.0 0.0 21.2 25.0 + 0 O dx2y2 0.5 0.0 49.7 0.0 0.0 0.0 + 0 O dxy 0.0 0.5 0.0 49.7 0.0 0.0 + 0 O f+1 0.0 0.0 0.0 0.0 2.0 1.7 + 0 O f-1 0.0 0.0 0.0 0.0 1.7 2.0 + 0 O f+2 49.5 0.0 0.3 0.0 0.0 0.0 + 0 O f-2 0.0 49.5 0.0 0.3 0.0 0.0 + 1 O dxz 0.0 0.0 0.0 0.0 25.0 21.2 + 1 O dyz 0.0 0.0 0.0 0.0 21.2 25.0 + 1 O dx2y2 0.5 0.0 49.7 0.0 0.0 0.0 + 1 O dxy 0.0 0.5 0.0 49.7 0.0 0.0 + 1 O f+1 0.0 0.0 0.0 0.0 2.0 1.7 + 1 O f-1 0.0 0.0 0.0 0.0 1.7 2.0 + 1 O f+2 49.5 0.0 0.3 0.0 0.0 0.0 + 1 O f-2 0.0 49.5 0.0 0.3 0.0 0.0 + + 84 85 86 87 88 89 + 7.47345 7.47345 7.75143 7.75143 7.96223 8.28986 + 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 + -------- -------- -------- -------- -------- -------- + 0 O s 0.0 0.0 0.0 0.0 3.1 7.9 + 0 O pz 0.0 0.0 0.0 0.0 1.7 8.1 + 0 O px 3.3 0.0 1.9 0.0 0.0 0.0 + 0 O py 0.0 3.3 0.0 1.9 0.0 0.0 + 0 O dz2 0.0 0.0 0.0 0.0 34.1 14.6 + 0 O dxz 46.5 0.0 1.9 0.0 0.0 0.0 + 0 O dyz 0.0 46.5 0.0 1.9 0.0 0.0 + 0 O f0 0.0 0.0 0.0 0.0 11.1 19.3 + 0 O f+1 0.2 0.0 46.1 0.0 0.0 0.0 + 0 O f-1 0.0 0.2 0.0 46.1 0.0 0.0 + 1 O s 0.0 0.0 0.0 0.0 3.1 7.9 + 1 O pz 0.0 0.0 0.0 0.0 1.7 8.1 + 1 O px 3.3 0.0 1.9 0.0 0.0 0.0 + 1 O py 0.0 3.3 0.0 1.9 0.0 0.0 + 1 O dz2 0.0 0.0 0.0 0.0 34.1 14.6 + 1 O dxz 46.5 0.0 1.9 0.0 0.0 0.0 + 1 O dyz 0.0 46.5 0.0 1.9 0.0 0.0 + 1 O f0 0.0 0.0 0.0 0.0 11.1 19.3 + 1 O f+1 0.2 0.0 46.1 0.0 0.0 0.0 + 1 O f-1 0.0 0.2 0.0 46.1 0.0 0.0 + + 90 91 + 12.57676 14.21504 + 0.00000 0.00000 + -------- -------- + 0 O s 42.5 41.9 + 0 O pz 3.3 5.8 + 0 O dz2 3.3 1.4 + 0 O f0 0.8 0.9 + 1 O s 42.5 41.9 + 1 O pz 3.3 5.8 + 1 O dz2 3.3 1.4 + 1 O f0 0.8 0.9 + +---------------------------- +LOEWDIN REDUCED ACTIVE MOs +---------------------------- + + 0 1 2 3 4 5 + -20.71707 -20.71608 -1.10301 -0.75414 -1.60387 -0.68793 + 2.00000 2.00000 2.00000 2.00000 2.00000 1.94379 + -------- -------- -------- -------- -------- -------- + 0 O s 49.0 49.1 20.9 7.4 45.9 0.0 + 0 O pz 0.3 0.2 30.1 27.8 7.4 0.0 + 0 O py 0.0 0.0 0.0 0.0 0.0 42.7 + 1 O s 49.0 49.1 35.2 19.7 19.4 0.0 + 1 O pz 0.3 0.2 4.7 40.9 19.7 0.0 + 1 O py 0.0 0.0 0.0 0.0 0.0 42.7 + + 6 7 8 9 10 11 + -0.68793 -0.22028 -0.22028 0.10041 0.14473 0.15467 + 1.94379 1.05621 1.05621 0.00000 0.00000 0.00000 + -------- -------- -------- -------- -------- -------- + 0 O s 0.0 0.0 0.0 1.6 38.8 0.0 + 0 O pz 0.0 0.0 0.0 47.4 10.8 0.0 + 0 O px 42.7 0.0 40.0 0.0 0.0 20.3 + 0 O py 3.4 40.0 0.0 0.0 0.0 29.3 + 0 O dxz 2.2 0.0 7.0 0.0 0.0 0.1 + 0 O dyz 0.2 7.0 0.0 0.0 0.0 0.1 + 1 O s 0.0 0.0 0.0 1.6 38.8 0.0 + 1 O pz 0.0 0.0 0.0 47.4 10.8 0.0 + 1 O px 42.7 0.0 40.0 0.0 0.0 20.3 + 1 O py 3.4 40.0 0.0 0.0 0.0 29.3 + 1 O dxz 2.2 0.0 7.0 0.0 0.0 0.1 + 1 O dyz 0.2 7.0 0.0 0.0 0.0 0.1 + +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.scfp +Input spin density ... input.scfr +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.000000 1.000000 + 1 O : 0.000000 1.000000 +Sum of atomic charges : 0.0000000 +Sum of atomic spin densities: 2.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.955102 s : 3.955102 + pz : 1.033371 p : 3.995782 + px : 1.481205 + py : 1.481205 + dz2 : 0.008746 d : 0.038506 + dxz : 0.014880 + dyz : 0.014880 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.002781 f : 0.010611 + f+1 : 0.003915 + f-1 : 0.003915 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 O s : 3.955102 s : 3.955102 + pz : 1.033371 p : 3.995782 + px : 1.481205 + py : 1.481205 + dz2 : 0.008746 d : 0.038506 + dxz : 0.014880 + dyz : 0.014880 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.002781 f : 0.010611 + f+1 : 0.003915 + f-1 : 0.003915 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.998893 + px : 0.499447 + py : 0.499447 + dz2 : 0.000000 d : -0.001142 + dxz : -0.000571 + dyz : -0.000571 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.002249 + f+1 : 0.001124 + f-1 : 0.001124 + f+2 : 0.000000 + f-2 : -0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.998893 + px : 0.499447 + py : 0.499447 + dz2 : 0.000000 d : -0.001142 + dxz : -0.000571 + dyz : -0.000571 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.002249 + f+1 : 0.001124 + f-1 : 0.001124 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : -0.000000 1.000000 + 1 O : 0.000000 1.000000 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.444799 s : 3.444799 + pz : 1.315927 p : 3.953749 + px : 1.318911 + py : 1.318911 + dz2 : 0.184502 d : 0.424528 + dxz : 0.120013 + dyz : 0.120013 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.054773 f : 0.176924 + f+1 : 0.061076 + f-1 : 0.061076 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 O s : 3.444799 s : 3.444799 + pz : 1.315927 p : 3.953749 + px : 1.318911 + py : 1.318911 + dz2 : 0.184502 d : 0.424528 + dxz : 0.120013 + dyz : 0.120013 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.054773 f : 0.176924 + f+1 : 0.061076 + f-1 : 0.061076 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + +SPIN + 0 O s : 0.000000 s : 0.000000 + pz : 0.000000 p : 0.807752 + px : 0.403876 + py : 0.403876 + dz2 : -0.000000 d : 0.134443 + dxz : 0.067221 + dyz : 0.067221 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : -0.000000 f : 0.057806 + f+1 : 0.028903 + f-1 : 0.028903 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + 1 O s : -0.000000 s : -0.000000 + pz : 0.000000 p : 0.807752 + px : 0.403876 + py : 0.403876 + dz2 : 0.000000 d : 0.134443 + dxz : 0.067221 + dyz : 0.067221 + dx2y2 : 0.000000 + dxy : 0.000000 + f0 : 0.000000 f : 0.057806 + f+1 : 0.028903 + f-1 : 0.028903 + f+2 : 0.000000 + f-2 : 0.000000 + f+3 : 0.000000 + f-3 : 0.000000 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.0000 8.0000 -0.0000 2.1340 1.4220 0.7121 + 1 O 8.0000 8.0000 0.0000 2.1340 1.4220 0.7121 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-O ) : 1.4220 + + +------------------------------------------------------------- + Forming the transition density ... done in 0.000239 sec +------------------------------------------------------------- + + + +========================================== +CASSCF UV, CD spectra and dipole moments +========================================== +------------------- +ABSORPTION SPECTRUM +------------------- + +Center of mass = ( 0.0000, 0.0000, 0.0000) +Nuclear contribution to the dipole moment = 0.000000, 0.000000, 0.000000 au + +Calculating the Dipole integrals ... done +Transforming integrals ... done +Calculating the Linear Momentum integrals ... done +Transforming integrals ... done +Calculating the Angular Momentum integrals ... done +Transforming integrals ... done + +------------------------------------------------------------------------------ + DIPOLE MOMENTS +------------------------------------------------------------------------------ + Root Block TX TY TZ |T| + (Debye) (Debye) (Debye) (Debye) +------------------------------------------------------------------------------ + 0 0 -0.00000 0.00000 -0.00000 0.00000 + +-------------- +CASSCF TIMINGS +-------------- + +Total time ... 2.2 sec +Sum of individual times ... 1.6 sec ( 74.3%) + +Calculation of AO operators + F(Core) operator ... 0.3 sec ( 14.6%) + G(Act) operator ... 0.4 sec ( 16.3%) + J(AO) operators ... 0.0 sec ( 0.0%) +Calculation of MO transformed quantities + J(MO) operators ... 0.9 sec ( 39.1%) + (pq|rs) integrals ... 0.0 sec ( 0.0%) + AO->MO one electron integrals ... 0.0 sec ( 0.1%) +Configuration interaction steps + CI-setup phase ... 0.0 sec ( 0.1%) + CI-solution phase ... 0.0 sec ( 1.5%) + Generation of densities ... 0.0 sec ( 0.1%) +Orbital improvement steps + Orbital gradient ... 0.0 sec ( 1.8%) + O(1) converger ... 0.0 sec ( 0.6%) +Properties ... 0.0 sec ( 0.0%) + SOC integral calculation ... 0.0 sec ( 0.0%) + SSC RMEs (incl. integrals) ... 0.0 sec ( 0.0%) + SOC RMEs ... 0.0 sec ( 0.0%) + +Maximum memory used throughout the entire CASSCF-calculation: 76.0 MB +Warning: no block have been defined for MRCI - copying CASSCF information! + + + ************************************************************ + * Program running with 16 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA MRCI +------------------------------------------------------------------------------ + +Transformed one-electron integrals ... input.cih.tmp +Transformed RI-integrals ... input.rijt.tmp +Output vectors ... input.mrci + +---------------- +MRCI-SETUP PHASE +---------------- + +GBW-Name ... input.gbw +IVO-Name ... input.ivo +HName ... input.H.tmp +SName ... input.S.tmp +CIHName ... input.cih.tmp +CIFName ... input.cif.tmp +MRCIName ... input.mrci +IntFiles ... input.rijt.tmp +LocName ... input.loc +MRCIInput ... input.mrciinp +Basis dimension ... 92 +Improved Virtual Orbitals ... OFF +Orbital localization ... OFF + +Figured out Orbital ranges +Set data to blocks + +----------------------- +FROZEN CORE FOCK MATRIX +----------------------- + +Improved virtual orbitals (IVOs) WILL NOT be constructed +Orbital Range is before PREP ... Int= 2- 1 Act= 2- 8 Ext= 9- 91 +Calculating Frozen Core Matrices ... (look at input.lastciprep) +Warning: FirstInternal=2 LastInternal=1 NInternals=0 - setting LastInternal for FI=-1 + +------------------------------------------------------------------------------ + ORCA CI-PREPARATION +------------------------------------------------------------------------------ +Reading the GBW file ... done + + +One-Electron Matrix ... input.H.tmp +GBW-File ... input.gbw +First MO in the CI ... 2 +Integral package used ... LIBINT +Reading the GBW file ... done + +Reading the one-electron matrix ... done +Forming inactive density ... done +Forming Fock matrix/matrices ... +Nuclear repulsion ... 27.867291 +Core repulsion ... 27.867291 +One-electron energy ... -141.599467 +Fock-energy ... -119.192360 +Final value ... -102.528623 +done +Transforming integrals ... done +Storing passive energy ... done ( -102.52862262 Eh) +The internal FI matrix is equal to the CIH matrix; storing it as such! + .... done with the Frozen Core Fock matrices +Final Orbital Range is now ... Int= 2- 1 Act= 2- 8 Ext= 9- 91 + +------------------------------ +PARTIAL COULOMB TRANSFORMATION +------------------------------ + +Dimension of the basis ... 92 +Number of internal MOs ... 90 (2-91) +Pair cutoff ... 2.500e-12 Eh +Number of AO pairs included in the trafo ... 4278 +Total Number of distinct AO pairs ... 4278 +Memory devoted for trafo ... 3200 MB +Memory needed per MO pair ... 0 MB +Max. Number of MO pairs treated together ... 98043 +Memory needed per MO ... 2 MB +Max. Number of MOs treated per batch ... 90 +Number Format for Storage ... Double (8 Byte) +Integral package used ... LIBINT + + --->>> The Coulomb operators (i,j|mue,nue) will be calculated + +Starting integral evaluation: +: : 22330 b 0 skpd 0.012 s ( 0.001 ms/b) +: 32480 b 0 skpd 0.011 s ( 0.000 ms/b) +: 24360 b 0 skpd 0.013 s ( 0.001 ms/b) +: 16240 b 0 skpd 0.016 s ( 0.001 ms/b) + 14616 b 0 skpd 0.010 s ( 0.001 ms/b) +: 19488 b 0 skpd 0.019 s ( 0.001 ms/b) +: 12992 b 0 skpd 0.017 s ( 0.001 ms/b) +: 8526 b 0 skpd 0.012 s ( 0.001 ms/b) +: 9744 b 0 skpd 0.022 s ( 0.002 ms/b) +: 4060 b 0 skpd 0.017 s ( 0.004 ms/b) +Collecting buffer AOJ + ... done with AO integral generation +Closing buffer AOJ ( 0.06 GB; CompressionRatio= 2.35) +Number of MO pairs included in the trafo ... 4095 + ... Now sorting integrals +IBATCH = 1 of 2 +IBATCH = 2 of 2 +Closing buffer JAO ( 0.13 GB; CompressionRatio= 1.00) +TOTAL TIME for half transformation ... 0.213 sec +AO-integral generation ... 0.112 sec +Half transformation ... 0.040 sec +J-integral sorting ... 0.060 sec +Collecting buffer JAO + +------------------- +FULL TRANSFORMATION +------------------- + +Processing MO 10 +Processing MO 20 +Processing MO 30 +Processing MO 40 +Processing MO 50 +Processing MO 60 +Processing MO 70 +Processing MO 80 +Processing MO 90 +Full transformation done +Number of integrals made ... 8386560 +Number of integrals stored ... 1944983 +Timings: +Time for first half transformation ... 0.221 sec +Time for second half transformation ... 0.043 sec +Total time ... 0.266 sec + +------------------ +CI-BLOCK STRUCTURE +------------------ + +Number of CI-blocks ... 1 + +=========== +CI BLOCK 1 +=========== +Multiplicity ... 3 +Irrep ... -1 +Number of reference defs ... 1 + Reference 1: CAS(12,7) + +Excitation type ... CISD +Excitation flags for singles: + 1 1 1 1 +Excitation flags for doubles: + 1 1 1 / 1 1 1 / 1 1 1 + + + + -------------------------------------------------------------------- + -------------------- ALL SETUP TASKS ACCOMPLISHED ------------------ + -------------------- ( 0.550 sec) ------------------ + -------------------------------------------------------------------- + + + + ################################################### + # # + # M R C I # + # # + # TSel = 1.000e-06 Eh # + # TPre = 1.000e-04 # + # TIntCut = 1.000e-10 Eh # + # Extrapolation to unselected MR-CI by full MP2 # + # DAVIDSON-1 Correction to full CI # + # # + ################################################### + + +--------------------- +INTEGRAL ORGANIZATION +--------------------- + +Reading the one-Electron matrix ... done +E0 read was -102.528622621202 +Reading the internal Fock matrix ... done +Preparing the integral list ... done +Loading the full integral list ... done +Making the simple integrals ... done + + *************************************** + * CI-BLOCK 1 * + *************************************** + +Configurations with insufficient # of SOMOs WILL be rejected +Building a CAS(12,7) for multiplicity 3 +Reference Space: + Initial Number of Configurations : 21 + Internal Orbitals : 2 - 1 + Active Orbitals : 2 - 8 + External Orbitals : 9 - 91 +The number of CSFs in the reference is 21 +Calling MRPT_Selection with N(ref)=21 +------------------ +REFERENCE SPACE CI +------------------ + + Pre-diagonalization threshold : 1.000e-04 +Warning: Setting NGuessMat to 512 +N(ref-CFG)=21 N(ref-CSF)=21 + + ****Iteration 0**** + Lowest Energy : -149.691723427995 + Maximum Energy change : 149.691723427995 (vector 0) + Maximum residual norm : 0.000000000000 + + *** CONVERGENCE OF RESIDUAL NORM REACHED *** +Reference space selection using TPre= 1.00e-04 + + ... found 2 reference configurations (2 CSFs) + ... now redoing the reference space CI ... + +Warning: Setting NGuessMat to 512 +N(ref-CFG)=2 N(ref-CSF)=2 + + ****Iteration 0**** + Lowest Energy : -149.691723427995 + Maximum Energy change : 149.691723427995 (vector 0) + Maximum residual norm : 0.000000000000 + + *** CONVERGENCE OF RESIDUAL NORM REACHED *** + +---------- +CI-RESULTS +---------- + +The threshold for printing is 0.30 percent +The weights of configurations will be printed. The weights are summed over +all CSFs that belong to a given configuration before printing + +STATE 0: Energy= -149.691723428 Eh RefWeight= 1.0000 0.00 eV 0.0 cm**-1 + 0.0562 : h---h---[2221122] + 0.9438 : h---h---[2222211] + +------------------------------ +MR-PT SELECTION TSel= 1.00e-06 +------------------------------ + + +Setting reference configurations WITHOUT use of symmetry +Building active patterns WITHOUT use of symmetry + +Selection will be done from 2 spatial configurations + ( 0) Refs : Sel: 2CFGs/ 2CSFs Gen: 2CFGs/ 2CSFs ( 0.000 sec) +Building active space densities ... 0.001 sec +Building active space Fock operators ... 0.003 sec + ( 1) (p,q)->(r,s): Sel: 19CFGs/ 19CSFs Gen: 19CFGs/ 19CSFs ( 0.001 sec) + ( 5) (p,-)->(a,-): Sel: 1162CFGs/ 2822CSFs Gen: 1162CFGs/ 2822CSFs ( 0.001 sec) + ( 6) (i,-)->(a,-): Sel: 0CFGs/ 0CSFs Gen: 0CFGs/ 0CSFs ( 0.001 sec) + ( 7) (i,j)->(p,a): Sel: 0CFGs/ 0CSFs Gen: 0CFGs/ 0CSFs ( 0.001 sec) + ( 8) (i,p)->(q,a): Sel: 0CFGs/ 0CSFs Gen: 0CFGs/ 0CSFs ( 0.001 sec) + ( 9) (p,q)->(r,a): Sel: 882CFGs/ 1950CSFs Gen: 4648CFGs/ 8632CSFs ( 0.001 sec) + (10) (i,p)->(a,b): Sel: 0CFGs/ 0CSFs Gen: 0CFGs/ 0CSFs ( 0.001 sec) + (11) (p,q)->(a,b): Sel: 13684CFGs/ 71990CSFs Gen: 177620CFGs/ 902210CSFs ( 0.005 sec) + (12) (i,j)->(a,b): Sel: 0CFGs/ 0CSFs Gen: 0CFGs/ 0CSFs ( 2.886 sec) + +Selection results: +Total number of generated configurations: 183451 +Number of selected configurations : 15749 ( 8.6%) +Total number of generated CSFs : 913685 +Number of selected CSFS : 76783 ( 8.4%) + +The selected tree structure: +Number of selected Internal Portions : 21 +Number of selected Singly External Portions: 70 + average number of VMOs/Portion : 28.79 + percentage of selected singly externals : 35.17 +Number of selected Doubly External Portions: 51 + average number of VMOs/Portion : 263.15 + percentage of selected doubly externals : 7.88 + +Diagonal second order perturbation results: +State E(tot) E(0)+E(1) E2(sel) E2(unsel) + Eh Eh Eh Eh +---------------------------------------------------------------- + 0 -150.134252690 -149.691723428 -0.430653 -0.011876 + +Computing the reference space Hamiltonian ... done (DIM=2) +Storing the reference space Hamiltonian ... done +Finding start and stop indices ... done +Collecting additional information ... done +Entering the DIIS solver section +------------------------ +MULTIROOT DIIS CI SOLVER +------------------------ + +Number of CSFs ... 76783 +Number of configurations ... 15749 +Maximum number of DIIS vectors stored ... 5 +Level shift ... 0.20 +Convergence tolerance on energies ... 2.500e-07 +Convergence tolerance on residual ... 2.500e-07 +Partitioning used ... MOELLER-PLESSET + + + ****Iteration 0**** + State 0: E= -150.060224186 Ec=-0.368500758 R= 0.132718631 W0= 0.90521 + Max energy change = 3.6850e-01 Eh + Max Residual Norm = 1.3272e-01 + + ****Iteration 1**** + State 0: E= -150.068098314 Ec=-0.383822151 R= 0.124176449 W0= 0.94176 + Max energy change = 7.8741e-03 Eh + Max Residual Norm = 1.2418e-01 + + ****Iteration 2**** + State 0: E= -150.087982244 Ec=-0.400243547 R= 0.002007987 W0= 0.92088 + Max energy change = 1.9884e-02 Eh + Max Residual Norm = 2.0080e-03 + + ****Iteration 3**** + State 0: E= -150.088905243 Ec=-0.403249019 R= 0.000636712 W0= 0.91536 + Max energy change = 9.2300e-04 Eh + Max Residual Norm = 6.3671e-04 + + ****Iteration 4**** + State 0: E= -150.089049239 Ec=-0.403891707 R= 0.000164690 W0= 0.91590 + Max energy change = 1.4400e-04 Eh + Max Residual Norm = 1.6469e-04 + + ****Iteration 5**** + State 0: E= -150.089165798 Ec=-0.405389830 R= 0.000013979 W0= 0.91512 + Max energy change = 1.1656e-04 Eh + Max Residual Norm = 1.3979e-05 + + ****Iteration 6**** + State 0: E= -150.089171183 Ec=-0.405649369 R= 0.000000731 W0= 0.91488 + Max energy change = 5.3853e-06 Eh + Max Residual Norm = 7.3075e-07 + + ****Iteration 7**** + State 0: residual converged + State 0: E= -150.089171468 Ec=-0.405710240 R= 0.000000114 W0= 0.91487 + Max energy change = 0.0000e+00 Eh + Max Residual Norm = 1.1401e-07 + *** Convergence of energies reached *** + *** Convergence of residual reached *** + *** All vectors converged *** +Returned from DIIS section + +---------------------------------------------- +MULTI-REFERENCE/MULTI-ROOT DAVIDSON CORRECTION +---------------------------------------------- + + +Summary of multireference corrections: + +Root W(ref) E(MR-CI) E(ref) Delta-E None Davidson-1 Davidson-2 Siegbahn Pople +------------------------------------------------------------------------------------------------------------ + 0 0.915 -150.089171468 -149.683461229 0.405710240 0.000000 -0.034537 -0.041623 -0.037750 -0.033493 +------------------------------------------------------------------------------------------------------------ +Active option = Davidson-1 + +Unselected CSF estimate: +Full relaxed MR-MP2 calculation ... + +Selection will be done from 2 spatial configurations + +Selection will be done from 2 spatial configurations + +Selection will be done from 2 spatial configurations +done +Selected MR-MP2 energies ... + + Root= 0 E(unsel)= -0.008732111 + +---------- +CI-RESULTS +---------- + +The threshold for printing is 0.30 percent +The weights of configurations will be printed. The weights are summed over +all CSFs that belong to a given configuration before printing + +STATE 0: Energy= -150.132440348 Eh RefWeight= 0.9149 0.00 eV 0.0 cm**-1 + 0.0154 : h---h---[2221122] + 0.8994 : h---h---[2222211] +Now choosing densities with flags StateDens=3 and TransDens=1 NStates(total)=1 +State density of the lowest state in each block NStateDens= 2 +GS to excited state transition electron densities NTransDens=0 +NDens(total)=2 +All lowest density information prepared Cnt(Dens)=2 +GS to ES state electron density information prepared Cnt(Dens)=2 + +------------------ +DENSITY GENERATION +------------------ + + ... generating densities (input.mrci.vec0) ... o.k. +MRCI-Population analysis: looping over 2 densities +Found state electron-density state=0 block=0 +Found state spin-density state=0 block=0 +------------------------------------------------------------------------------ + ORCA POPULATION ANALYSIS +------------------------------------------------------------------------------ +Input electron density ... input.state_0_block_0.el.tmp +Input spin density ... input.state_0_block_0.spin.tmp +BaseName (.gbw .S,...) ... input + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +------------------------------------------ +MULLIKEN ATOMIC CHARGES AND SPIN DENSITIES +------------------------------------------ + 0 O : -0.004821 0.997897 + 1 O : 0.004821 1.002103 +Sum of atomic charges : -0.0000000 +Sum of atomic spin densities: 2.0000000 + +--------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +--------------------------------------------------- +CHARGE + 0 O s : 3.956860 s : 3.956860 + pz : 1.028405 p : 3.971209 + px : 1.471401 + py : 1.471404 + dz2 : 0.009877 d : 0.064047 + dxz : 0.022565 + dyz : 0.022561 + dx2y2 : 0.004525 + dxy : 0.004519 + f0 : 0.002561 f : 0.012705 + f+1 : 0.004197 + f-1 : 0.004197 + f+2 : 0.000490 + f-2 : 0.000491 + f+3 : 0.000385 + f-3 : 0.000385 + 1 O s : 3.950779 s : 3.950779 + pz : 1.025302 p : 3.967429 + px : 1.471062 + py : 1.471066 + dz2 : 0.009918 d : 0.064204 + dxz : 0.022733 + dyz : 0.022729 + dx2y2 : 0.004412 + dxy : 0.004412 + f0 : 0.002565 f : 0.012766 + f+1 : 0.004231 + f-1 : 0.004231 + f+2 : 0.000491 + f-2 : 0.000491 + f+3 : 0.000379 + f-3 : 0.000379 + +SPIN + 0 O s : 0.011152 s : 0.011152 + pz : -0.006700 p : 0.987931 + px : 0.497311 + py : 0.497320 + dz2 : 0.001400 d : -0.001521 + dxz : -0.002888 + dyz : -0.002895 + dx2y2 : 0.001435 + dxy : 0.001428 + f0 : -0.000178 f : 0.000336 + f+1 : 0.000111 + f-1 : 0.000109 + f+2 : 0.000038 + f-2 : 0.000039 + f+3 : 0.000108 + f-3 : 0.000108 + 1 O s : 0.009819 s : 0.009819 + pz : -0.005407 p : 0.993246 + px : 0.499322 + py : 0.499331 + dz2 : 0.001198 d : -0.001330 + dxz : -0.002663 + dyz : -0.002669 + dx2y2 : 0.001403 + dxy : 0.001401 + f0 : -0.000206 f : 0.000368 + f+1 : 0.000150 + f-1 : 0.000148 + f+2 : 0.000031 + f-2 : 0.000029 + f+3 : 0.000107 + f-3 : 0.000107 + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +----------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN DENSITIES +----------------------------------------- + 0 O : -0.000197 0.998944 + 1 O : 0.000197 1.001056 + +-------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN DENSITIES +-------------------------------------------------- +CHARGE + 0 O s : 3.443404 s : 3.443404 + pz : 1.305012 p : 3.934071 + px : 1.314529 + py : 1.314530 + dz2 : 0.188355 d : 0.445749 + dxz : 0.124289 + dyz : 0.124287 + dx2y2 : 0.004412 + dxy : 0.004406 + f0 : 0.055813 f : 0.176972 + f+1 : 0.059594 + f-1 : 0.059594 + f+2 : 0.000599 + f-2 : 0.000601 + f+3 : 0.000385 + f-3 : 0.000385 + 1 O s : 3.442969 s : 3.442969 + pz : 1.306626 p : 3.934218 + px : 1.313795 + py : 1.313796 + dz2 : 0.188268 d : 0.445602 + dxz : 0.124363 + dyz : 0.124361 + dx2y2 : 0.004305 + dxy : 0.004304 + f0 : 0.055820 f : 0.177015 + f+1 : 0.059617 + f-1 : 0.059618 + f+2 : 0.000602 + f-2 : 0.000601 + f+3 : 0.000378 + f-3 : 0.000378 + +SPIN + 0 O s : 0.009987 s : 0.009987 + pz : -0.010265 p : 0.790615 + px : 0.400439 + py : 0.400441 + dz2 : 0.004106 d : 0.139311 + dxz : 0.066218 + dyz : 0.066215 + dx2y2 : 0.001389 + dxy : 0.001384 + f0 : 0.001487 f : 0.059031 + f+1 : 0.028579 + f-1 : 0.028579 + f+2 : 0.000085 + f-2 : 0.000085 + f+3 : 0.000108 + f-3 : 0.000108 + 1 O s : 0.010098 s : 0.010098 + pz : -0.009833 p : 0.793084 + px : 0.401457 + py : 0.401460 + dz2 : 0.004034 d : 0.138984 + dxz : 0.066122 + dyz : 0.066119 + dx2y2 : 0.001355 + dxy : 0.001354 + f0 : 0.001465 f : 0.058890 + f+1 : 0.028529 + f-1 : 0.028529 + f+2 : 0.000078 + f-2 : 0.000075 + f+3 : 0.000108 + f-3 : 0.000108 + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 O 8.0048 8.0000 -0.0048 2.3173 1.3999 0.9173 + 1 O 7.9952 8.0000 0.0048 2.3185 1.3999 0.9185 + + Mayer bond orders larger than 0.100000 +B( 0-O , 1-O ) : 1.3999 + + +--------------------- +CI-EXCITATION SPECTRA +--------------------- + +Center of mass = ( 0.0000, 0.0000, 0.0000) + +Nuclear contribution to the dipole moment= 0.000000, 0.000000, 0.000000 au + +Calculating the Dipole integrals ... done +Transforming integrals ... done +Calculating the Linear Momentum integrals ... done +Transforming integrals ... done +Calculating the Angular momentum integrals ... done +Transforming integrals ... done + +------------------------------------------------------------------------------------------ + ABSORPTION SPECTRUM +------------------------------------------------------------------------------------------ + States Energy Wavelength fosc T2 TX TY TZ + (cm-1) (nm) (D**2) (D) (D) (D) +------------------------------------------------------------------------------------------ + +------------------------------------------------------------------------------ + CD SPECTRUM +------------------------------------------------------------------------------ + States Energy Wavelength R*T RX RY RZ + (cm-1) (nm) (1e40*sgs) (au) (au) (au) +------------------------------------------------------------------------------ + +------------------------------------------------------------------------------ + STATE DIPOLE MOMENTS +------------------------------------------------------------------------------ + Root Block TX TY TZ |T| + (Debye) (Debye) (Debye) (Debye) +------------------------------------------------------------------------------ + 0 0 -0.00000 0.00000 -0.00515 0.00515 + +Maximum memory used throughout the entire MRCI-calculation: 114.3 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -150.132440347903 +------------------------- -------------------- + + + *************************************** + * ORCA property calculations * + *************************************** + + --------------------- + Active property flags + --------------------- + (+) Dipole Moment + + +------------------------------------------------------------------------------ + ORCA ELECTRIC PROPERTIES CALCULATION +------------------------------------------------------------------------------ + +Dipole Moment Calculation ... on +Quadrupole Moment Calculation ... off +Polarizability Calculation ... off +GBWName ... input.gbw +Electron density ... input.scfp +The origin for moment calculation is the CENTER OF MASS = ( 0.000000, 0.000000 0.000000) + +------------- +DIPOLE MOMENT +------------- + X Y Z +Electronic contribution: -0.00000 0.00000 -0.00000 +Nuclear contribution : 0.00000 0.00000 0.00000 + ----------------------------------------- +Total Dipole Moment : -0.00000 0.00000 -0.00000 + ----------------------------------------- +Magnitude (a.u.) : 0.00000 +Magnitude (Debye) : 0.00000 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 0.000000 1.426794 1.426794 +Rotational constants in MHz : 0.000000 42774.214970 42774.214970 + + Dipole components along the rotational axes: +x,y,z [a.u.] : -0.000000 0.000000 -0.000000 +x,y,z [Debye]: -0.000000 0.000000 -0.000000 + + + +Timings for individual modules: + +Sum of individual times ... 23.135 sec (= 0.386 min) +GTO integral calculation ... 5.378 sec (= 0.090 min) 23.2 % +SCF iterations ... 0.931 sec (= 0.016 min) 4.0 % +CASSCF iterations ... 5.369 sec (= 0.089 min) 23.2 % +Multireference CI module ... 11.456 sec (= 0.191 min) 49.5 % + ****ORCA TERMINATED NORMALLY**** +TOTAL RUN TIME: 0 days 0 hours 0 minutes 25 seconds 879 msec From 0a8303f7287542f639e19ee47ddd7298b94c98ef Mon Sep 17 00:00:00 2001 From: Alon Grinberg Dana Date: Mon, 19 Aug 2024 19:30:16 +0300 Subject: [PATCH 10/16] Added reaction MRCI example and organised other examples into Reactions and Stationary subfolders --- examples/Reactions/MRCI/TS0.xyz | 7 ++++++ examples/Reactions/MRCI/input.yml | 24 +++++++++++++++++++ examples/{ => Reactions}/rates_demo/input.yml | 0 examples/{ => Stationary}/TS/input.yml | 0 examples/{ => Stationary}/bde/input.yml | 0 .../{ => Stationary}/thermo_demo/input.yml | 0 6 files changed, 31 insertions(+) create mode 100644 examples/Reactions/MRCI/TS0.xyz create mode 100644 examples/Reactions/MRCI/input.yml rename examples/{ => Reactions}/rates_demo/input.yml (100%) rename examples/{ => Stationary}/TS/input.yml (100%) rename examples/{ => Stationary}/bde/input.yml (100%) rename examples/{ => Stationary}/thermo_demo/input.yml (100%) diff --git a/examples/Reactions/MRCI/TS0.xyz b/examples/Reactions/MRCI/TS0.xyz new file mode 100644 index 0000000000..a617a6d0c0 --- /dev/null +++ b/examples/Reactions/MRCI/TS0.xyz @@ -0,0 +1,7 @@ +5 +TS0 optimized at b2plypd3/aug-cc-pvtz +N -0.00000000 -1.36720300 0.15499300 +O -0.00000000 -1.10333100 -0.98685800 +H -0.00000000 -0.28110100 0.76732400 +O 0.00000000 0.97476200 0.91364300 +O 0.00000000 1.44007500 -0.27062400 diff --git a/examples/Reactions/MRCI/input.yml b/examples/Reactions/MRCI/input.yml new file mode 100644 index 0000000000..08cde6cbb8 --- /dev/null +++ b/examples/Reactions/MRCI/input.yml @@ -0,0 +1,24 @@ +project: MRCI_reaction_example + +level_of_theory: MP2_CASSCF_MRCI/aug-cc-pVTZ//B2PLYPD3/aug-cc-pVTZ + +ts_adapters: [] + +job_memory: 50 + +compute_thermo: false + +species: + - label: HNO + smiles: 'N=O' + - label: O2 + smiles: '[O][O]' + - label: 'NO' + smiles: '[N]=O' + - label: HO2 + smiles: 'O[O]' + +reactions: + - label: HNO + O2 <=> NO + HO2 + multiplicity: 3 + xyz: ['TS0.xyz'] diff --git a/examples/rates_demo/input.yml b/examples/Reactions/rates_demo/input.yml similarity index 100% rename from examples/rates_demo/input.yml rename to examples/Reactions/rates_demo/input.yml diff --git a/examples/TS/input.yml b/examples/Stationary/TS/input.yml similarity index 100% rename from examples/TS/input.yml rename to examples/Stationary/TS/input.yml diff --git a/examples/bde/input.yml b/examples/Stationary/bde/input.yml similarity index 100% rename from examples/bde/input.yml rename to examples/Stationary/bde/input.yml diff --git a/examples/thermo_demo/input.yml b/examples/Stationary/thermo_demo/input.yml similarity index 100% rename from examples/thermo_demo/input.yml rename to examples/Stationary/thermo_demo/input.yml From dcff101a7346b3be1b11ef8617da435bd086f61a Mon Sep 17 00:00:00 2001 From: Alon Grinberg Dana Date: Mon, 19 Aug 2024 19:46:22 +0300 Subject: [PATCH 11/16] Docs: Documented the new MRCI feature --- docs/source/advanced.rst | 25 +++++++++++++++++++++++++ 1 file changed, 25 insertions(+) diff --git a/docs/source/advanced.rst b/docs/source/advanced.rst index 37c94e1a7a..bcf65c6090 100644 --- a/docs/source/advanced.rst +++ b/docs/source/advanced.rst @@ -185,6 +185,31 @@ Another example:: will append ``iop(99/33=1)`` to the respective Gaussian job input file. +To request a multireference calculation, such as MRCI, one can specify any of the following examples: + +- A "simple" MRCI computation (text example):: + + sp_level = 'MRCI/cc-pVTZ' + + - Adding explicitly correlated calculations (F12) which provide improvement of the basis set convergence. +Only available through Molpro (dictionary example):: + + sp_level = {'method': 'MRCI-F12', 'basis': 'cc-pVTZ-F12} + +Users can also specify a chain of jobs to be performed (supported in Molpro and Orca) so that the MRCI +calculation uses the orbitals of the previous job. For example, to perform a MRCI calculation on CASSCF orbitals, +one can specify:: + + sp_level = {'method': 'MP2_CASSCF_MRCI', 'basis': 'aug-cc-pVTZ'} + +This chain, seperated by underscores, will perform an HF calculation (by default, no need to specify), +an MP2 calculation, then a CASSCF calculation, and finally an MRCI calculation on CASSCF orbitals. +Note that requesting an MRCI job will cause ARC to first automatically spawn a Molpro CCSD/cc-pVDZ job to identify +the active space for the MRCI calculation. If the subsequent job is spawned in Orca, the active space will be used. +If the subsequent MRCI job is spawned in Molpro, the entire space is currently considered (the active space is not +determined explicitly). It is therefore recommended to set the ``levels_ess`` dict in settings to that "MRCI" jobs +will be executed in Orca, and "F12" and "CCSD" jobs will be executed in Molpro. + Adaptive levels of theory ^^^^^^^^^^^^^^^^^^^^^^^^^ From f94bf6f7ee38d1bc1d7186453b911b77a9b62ead Mon Sep 17 00:00:00 2001 From: Alon Grinberg Dana Date: Tue, 3 Sep 2024 07:46:18 +0300 Subject: [PATCH 12/16] Added CASPT2 (RS2C) multireference support for Molpro --- arc/job/adapters/molpro.py | 6 +++--- arc/scheduler.py | 7 ++++--- 2 files changed, 7 insertions(+), 6 deletions(-) diff --git a/arc/job/adapters/molpro.py b/arc/job/adapters/molpro.py index 9b6e3b7820..dcd6925c49 100644 --- a/arc/job/adapters/molpro.py +++ b/arc/job/adapters/molpro.py @@ -249,7 +249,7 @@ def write_input_file(self) -> None: if 'IGNORE_ERROR in the ORBITAL directive' in self.args['trsh'].keys(): keywords.append('ORBITAL,IGNORE_ERROR') - if 'mrci' in self.level.method: + if 'mrci' in self.level.method or 'rs2' in self.level.method: input_dict['orbitals'] = '\ngprint,orbitals;\n' input_dict['restricted'] = '' if '_' in self.level.method: @@ -268,8 +268,8 @@ def write_input_file(self) -> None: {{mrci{"-f12" if "f12" in self.level.method.lower() else ""}; maxit,999; wf,spin={input_dict['spin']},charge={input_dict['charge']};}}""" - - input_dict['block'] += '\n\nE_mrci=energy;\nE_mrci_Davidson=energd;\n\ntable,E_mrci,E_mrci_Davidson;' + if 'mrci' in self.level.method: + input_dict['block'] += '\n\nE_mrci=energy;\nE_mrci_Davidson=energd;\n\ntable,E_mrci,E_mrci_Davidson;' input_dict = update_input_dict_with_args(args=self.args, input_dict=input_dict) diff --git a/arc/scheduler.py b/arc/scheduler.py index 7a6a9ce841..ac2b199313 100644 --- a/arc/scheduler.py +++ b/arc/scheduler.py @@ -1295,14 +1295,14 @@ def run_sp_job(self, self.job_dict[label]['sp'] = dict() if self.composite_method: raise SchedulerError(f'run_sp_job() was called for {label} which has a composite method level of theory') - if 'mrci' in level.method: + if 'mrci' in level.method or 'rs2' in level.method: if self.job_dict[label]['sp']: if self.species_dict[label].active is None: self.species_dict[label].active = parser.parse_active_space( sp_path=self.output[label]['paths']['sp'], species=self.species_dict[label]) else: - logger.info(f'Running a CCSD/cc-pVDZ job for {label} before the MRCI job') + logger.info(f'Running a CCSD/cc-pVDZ job for {label} before the multireference job') self.run_job(label=label, xyz=self.species_dict[label].get_xyz(generate=False), level_of_theory='ccsd/cc-pvdz', @@ -2629,7 +2629,8 @@ def check_sp_job(self, label (str): The species label. job (JobAdapter): The single point job object. """ - if 'mrci' in self.sp_level.method and job.level is not None and 'mrci' not in job.level.method: + if ('mrci' in self.sp_level.method or 'rs2' in self.sp_level.method) and job.level is not None \ + and 'mrci' not in job.level.method and 'rs2' not in job.level.method: self.output[label]['paths']['sp'] = job.local_path_to_output_file self.run_sp_job(label) elif job.job_status[1]['status'] == 'done': From 410e9122fe66cfd10585da054e396fcd57778653 Mon Sep 17 00:00:00 2001 From: Alon Grinberg Dana Date: Tue, 3 Sep 2024 07:46:50 +0300 Subject: [PATCH 13/16] Removed MRCI from inputs.py --- arc/settings/inputs.py | 33 +-------------------------------- 1 file changed, 1 insertion(+), 32 deletions(-) diff --git a/arc/settings/inputs.py b/arc/settings/inputs.py index b043582cfb..cabf236db9 100644 --- a/arc/settings/inputs.py +++ b/arc/settings/inputs.py @@ -2,38 +2,7 @@ Input files """ -input_files = { - 'mrci': """***,name -memory,{memory},m; -geometry={{angstrom; -{xyz}}} - -gprint,orbitals; - -basis={basis} - -{{hf;shift,-1.0,-0.5; -maxit,1000; -wf,spin={spin},charge={charge};}} - -{{multi; -{occ}noextra,failsafe,config,csf; -wf,spin={spin},charge={charge}; -natorb,print,ci;}} - -{{mrci; -{occ}wf,spin={spin},charge={charge};}} - -E_mrci=energy; -E_mrci_Davidson=energd; - -table,E_mrci,E_mrci_Davidson; - ----; - -""", - - 'arkane_input_species': """#!/usr/bin/env python3 +input_files = {'arkane_input_species': """#!/usr/bin/env python3 # encoding: utf-8 {bonds}externalSymmetry = {symmetry} From 62da0bb18efb29c50cd078a3b61202830531e7bc Mon Sep 17 00:00:00 2001 From: Alon Grinberg Dana Date: Sat, 7 Sep 2024 22:37:39 +0300 Subject: [PATCH 14/16] Always print NATURAL ORBITALS in Molpro --- arc/job/adapters/molpro.py | 3 +-- 1 file changed, 1 insertion(+), 2 deletions(-) diff --git a/arc/job/adapters/molpro.py b/arc/job/adapters/molpro.py index dcd6925c49..8a7fe9a47b 100644 --- a/arc/job/adapters/molpro.py +++ b/arc/job/adapters/molpro.py @@ -211,7 +211,6 @@ def write_input_file(self) -> None: 'keywords', 'memory', 'method', - 'orbitals', 'restricted', ]: input_dict[key] = '' @@ -226,6 +225,7 @@ def write_input_file(self) -> None: input_dict['shift'] = self.args['trsh']['shift'] if 'shift' in self.args['trsh'].keys() else '' input_dict['spin'] = self.multiplicity - 1 input_dict['xyz'] = xyz_to_str(self.xyz) + input_dict['orbitals'] = '\ngprint,orbitals;\n' if not is_restricted(self): input_dict['restricted'] = 'u' @@ -250,7 +250,6 @@ def write_input_file(self) -> None: keywords.append('ORBITAL,IGNORE_ERROR') if 'mrci' in self.level.method or 'rs2' in self.level.method: - input_dict['orbitals'] = '\ngprint,orbitals;\n' input_dict['restricted'] = '' if '_' in self.level.method: methods = self.level.method.split('_') From 96f78bb123b96873aba0ae3944718bae5dd4bfd7 Mon Sep 17 00:00:00 2001 From: Alon Grinberg Dana Date: Sun, 8 Sep 2024 09:25:20 +0300 Subject: [PATCH 15/16] Use occ and closed in Molpro --- arc/job/adapters/molpro.py | 38 ++++++++++++++++++++++++++++---------- 1 file changed, 28 insertions(+), 10 deletions(-) diff --git a/arc/job/adapters/molpro.py b/arc/job/adapters/molpro.py index 8a7fe9a47b..a08f708c99 100644 --- a/arc/job/adapters/molpro.py +++ b/arc/job/adapters/molpro.py @@ -45,11 +45,13 @@ ${auxiliary_basis} ${cabs} int; + {hf;${shift} maxit,999; - wf,spin=${spin},charge=${charge};} + wf,spin=${spin},charge=${charge}; +} -${restricted}${method}; +${restricted}${method} ${job_type_1} ${job_type_2}${block} @@ -221,7 +223,7 @@ def write_input_file(self) -> None: input_dict['charge'] = self.charge input_dict['label'] = self.species_label input_dict['memory'] = self.input_file_memory - input_dict['method'] = self.level.method + input_dict['method'] = f'{self.level.method};' input_dict['shift'] = self.args['trsh']['shift'] if 'shift' in self.args['trsh'].keys() else '' input_dict['spin'] = self.multiplicity - 1 input_dict['xyz'] = xyz_to_str(self.xyz) @@ -247,26 +249,42 @@ def write_input_file(self) -> None: pass if 'IGNORE_ERROR in the ORBITAL directive' in self.args['trsh'].keys(): - keywords.append('ORBITAL,IGNORE_ERROR') + keywords.append(' ORBITAL,IGNORE_ERROR;') if 'mrci' in self.level.method or 'rs2' in self.level.method: + active = self.species[0].active input_dict['restricted'] = '' if '_' in self.level.method: methods = self.level.method.split('_') input_dict['method'] = '' for method in methods: - input_dict['method'] += '\n\n{' + method.lower() + ';\n' + input_dict['method'] += '\n{' + method.lower() + ';\n' if 'mp2' not in method.lower(): input_dict['method'] += ' maxit,999;\n' - input_dict['method'] += f' wf,spin={input_dict["spin"]},charge={input_dict["charge"]};' + '}' + input_dict['method'] += f' wf,spin={input_dict["spin"]},charge={input_dict["charge"]};\n' + if 'casscf' in method.lower() and active is not None: + if 'occ' in active: + input_dict['method'] += f' occ,{",".join([str(i) for i in active["occ"]])};\n' + if 'closed' in active: + input_dict['method'] += f' closed,{",".join([str(i) for i in active["closed"]])};\n' + input_dict['method'] += ' state,1;\n' # ground state + input_dict['method'] += '}\n' else: input_dict['method'] = f"""{{casscf; maxit,999; - wf,spin={input_dict['spin']},charge={input_dict['charge']};}} - -{{mrci{"-f12" if "f12" in self.level.method.lower() else ""}; + wf,spin={input_dict['spin']},charge={input_dict['charge']}; +""" + if active is not None: + if 'occ' in active: + input_dict['method'] += f' occ,{",".join([str(i) for i in active["occ"]])};\n' + if 'closed' in active: + input_dict['method'] += f' closed,{",".join([str(i) for i in active["closed"]])};\n' + input_dict['method'] += ' state,1;\n' # ground state + input_dict['method'] += '}\n\n' + input_dict['method'] += f"""{{mrci{"-f12" if "f12" in self.level.method.lower() else ""}; maxit,999; - wf,spin={input_dict['spin']},charge={input_dict['charge']};}}""" + wf,spin={input_dict['spin']},charge={input_dict['charge']}; +}}""" if 'mrci' in self.level.method: input_dict['block'] += '\n\nE_mrci=energy;\nE_mrci_Davidson=energd;\n\ntable,E_mrci,E_mrci_Davidson;' From 2876e24d7c5ca3273178ed9dc48f6d1eb3073bc9 Mon Sep 17 00:00:00 2001 From: Alon Grinberg Dana Date: Mon, 19 Aug 2024 13:43:00 +0300 Subject: [PATCH 16/16] Tests: Molpro input files MRCI and CASPT2 (RS2C) --- arc/job/adapters/molpro_test.py | 333 ++++++++++++++++++++++++++++++-- 1 file changed, 321 insertions(+), 12 deletions(-) diff --git a/arc/job/adapters/molpro_test.py b/arc/job/adapters/molpro_test.py index a69b036c62..a7dc828353 100644 --- a/arc/job/adapters/molpro_test.py +++ b/arc/job/adapters/molpro_test.py @@ -42,6 +42,56 @@ def setUpClass(cls): species=[ARCSpecies(label='spc1', xyz=['O 0 0 1'])], testing=True, ) + cls.job_3 = MolproAdapter(execution_type='queue', + job_type='sp', + level=Level(method='MRCI', basis='aug-cc-pvtz-f12'), + project='test', + project_directory=os.path.join(ARC_PATH, 'arc', 'testing', 'test_MolproAdapter_3'), + species=[ARCSpecies(label='HNO_t', xyz=["""N -0.08142 0.37454 0.00000 + O 1.01258 -0.17285 0.00000 + H -0.93116 -0.20169 0.00000"""])], + testing=True, + ) + cls.job_4 = MolproAdapter(execution_type='queue', + job_type='sp', + level=Level(method='MRCI-F12', basis='aug-cc-pvtz-f12'), + project='test', + project_directory=os.path.join(ARC_PATH, 'arc', 'testing', 'test_MolproAdapter_4'), + species=[ARCSpecies(label='HNO_t', xyz=["""N -0.08142 0.37454 0.00000 + O 1.01258 -0.17285 0.00000 + H -0.93116 -0.20169 0.00000"""])], + testing=True, + ) + cls.job_5 = MolproAdapter(execution_type='queue', + job_type='sp', + level=Level(method='MP2_CASSCF_MRCI-F12', basis='aug-cc-pVTZ-F12'), + project='test', + project_directory=os.path.join(ARC_PATH, 'arc', 'testing', 'test_MolproAdapter_5'), + species=[ARCSpecies(label='HNO_t', xyz=["""N -0.08142 0.37454 0.00000 + O 1.01258 -0.17285 0.00000 + H -0.93116 -0.20169 0.00000"""])], + testing=True, + ) + cls.job_6 = MolproAdapter(execution_type='queue', + job_type='sp', + level=Level(method='MP2_CASSCF_RS2C', basis='aug-cc-pVTZ'), # CASPT2 + project='test', + project_directory=os.path.join(ARC_PATH, 'arc', 'testing', 'test_MolproAdapter_6'), + species=[ARCSpecies(label='HNO_t', xyz=["""N -0.08142 0.37454 0.00000 + O 1.01258 -0.17285 0.00000 + H -0.93116 -0.20169 0.00000"""])], + testing=True, + ) + cls.job_7 = MolproAdapter(execution_type='queue', + job_type='sp', + level=Level(method='MP2_CASSCF_RS2C', basis='aug-cc-pVTZ'), # CASPT2 + project='test', + project_directory=os.path.join(ARC_PATH, 'arc', 'testing', 'test_MolproAdapter_7'), + species=[ARCSpecies(label='N', xyz=["""N 0.0 0.0 0.0"""], + active={'occ': [3, 1, 1, 0, 1, 0, 0, 0], + 'closed': [1, 0, 0, 0, 0, 0, 0, 0]})], + testing=True, + ) def test_set_cpu_and_mem(self): """Test assigning number of cpu's and memory""" @@ -56,38 +106,42 @@ def test_set_input_file_memory(self): self.job_1.input_file_memory = None self.job_1.cpu_cores = 48 self.job_1.set_input_file_memory() - self.assertEqual(self.job_1.input_file_memory, 40) + self.assertEqual(self.job_1.input_file_memory, 438) self.job_1.cpu_cores = 8 self.job_1.set_input_file_memory() - self.assertEqual(self.job_1.input_file_memory, 235) + self.assertEqual(self.job_1.input_file_memory, 438) self.job_1.input_file_memory = None self.job_1.cpu_cores = 1 self.job_1.set_input_file_memory() - self.assertEqual(self.job_1.input_file_memory, 1880) + self.assertEqual(self.job_1.input_file_memory, 438) def test_write_input_file(self): - """Test writing Gaussian input files""" + """Test writing Molpro input files""" self.job_1.cpu_cores = 48 self.job_1.set_input_file_memory() self.job_1.write_input_file() with open(os.path.join(self.job_1.local_path, input_filenames[self.job_1.job_adapter]), 'r') as f: content_1 = f.read() job_1_expected_input_file = """***,spc1 -memory,40,m; +memory,Total=438,m; geometry={angstrom; O 0.00000000 0.00000000 1.00000000} +gprint,orbitals; + basis=cc-pvtz-f12 int; + {hf; -maxit,1000; -wf,spin=2,charge=0;} + maxit,999; + wf,spin=2,charge=0; +} uccsd(t)-f12; @@ -104,19 +158,23 @@ def test_write_input_file(self): with open(os.path.join(self.job_2.local_path, input_filenames[self.job_2.job_adapter]), 'r') as f: content_2 = f.read() job_2_expected_input_file = """***,spc1 -memory,40,m; +memory,Total=438,m; geometry={angstrom; O 0.00000000 0.00000000 1.00000000} +gprint,orbitals; + basis=cc-pvqz int; + {hf; -maxit,1000; -wf,spin=2,charge=0;} + maxit,999; + wf,spin=2,charge=0; +} uccsd(t); @@ -127,6 +185,257 @@ def test_write_input_file(self): """ self.assertEqual(content_2, job_2_expected_input_file) + def test_write_mrci_input_file(self): + """Test writing MRCI Molpro input files""" + self.job_3.cpu_cores = 48 + self.job_3.set_input_file_memory() + self.job_3.write_input_file() + with open(os.path.join(self.job_3.local_path, input_filenames[self.job_3.job_adapter]), 'r') as f: + content_3 = f.read() + job_3_expected_input_file = """***,HNO_t +memory,Total=438,m; + +geometry={angstrom; +N -0.08142000 0.37454000 0.00000000 +O 1.01258000 -0.17285000 0.00000000 +H -0.93116000 -0.20169000 0.00000000} + +gprint,orbitals; + +basis=aug-cc-pvtz-f12 + + + +int; + +{hf; + maxit,999; + wf,spin=0,charge=0; +} + +{casscf; + maxit,999; + wf,spin=0,charge=0; +} + +{mrci; + maxit,999; + wf,spin=0,charge=0; +} + + + + +E_mrci=energy; +E_mrci_Davidson=energd; + +table,E_mrci,E_mrci_Davidson; +---; + +""" + self.assertEqual(content_3, job_3_expected_input_file) + + self.job_4.cpu_cores = 48 + self.job_4.set_input_file_memory() + self.job_4.write_input_file() + with open(os.path.join(self.job_4.local_path, input_filenames[self.job_4.job_adapter]), 'r') as f: + content_4 = f.read() + job_4_expected_input_file = """***,HNO_t +memory,Total=438,m; + +geometry={angstrom; +N -0.08142000 0.37454000 0.00000000 +O 1.01258000 -0.17285000 0.00000000 +H -0.93116000 -0.20169000 0.00000000} + +gprint,orbitals; + +basis=aug-cc-pvtz-f12 + + + +int; + +{hf; + maxit,999; + wf,spin=0,charge=0; +} + +{casscf; + maxit,999; + wf,spin=0,charge=0; +} + +{mrci-f12; + maxit,999; + wf,spin=0,charge=0; +} + + + + +E_mrci=energy; +E_mrci_Davidson=energd; + +table,E_mrci,E_mrci_Davidson; +---; + +""" + self.assertEqual(content_4, job_4_expected_input_file) + + self.job_5.cpu_cores = 48 + self.job_5.set_input_file_memory() + self.job_5.write_input_file() + with open(os.path.join(self.job_5.local_path, input_filenames[self.job_5.job_adapter]), 'r') as f: + content_5 = f.read() + job_5_expected_input_file = """***,HNO_t +memory,Total=438,m; + +geometry={angstrom; +N -0.08142000 0.37454000 0.00000000 +O 1.01258000 -0.17285000 0.00000000 +H -0.93116000 -0.20169000 0.00000000} + +gprint,orbitals; + +basis=aug-cc-pvtz-f12 + + + +int; + +{hf; + maxit,999; + wf,spin=0,charge=0; +} + + +{mp2; + wf,spin=0,charge=0; +} + +{casscf; + maxit,999; + wf,spin=0,charge=0; +} + +{mrci-f12; + maxit,999; + wf,spin=0,charge=0; +} + + + + + +E_mrci=energy; +E_mrci_Davidson=energd; + +table,E_mrci,E_mrci_Davidson; +---; + +""" + self.assertEqual(content_5, job_5_expected_input_file) + + self.job_6.cpu_cores = 48 + self.job_6.set_input_file_memory() + self.job_6.write_input_file() + with open(os.path.join(self.job_6.local_path, input_filenames[self.job_6.job_adapter]), 'r') as f: + content_6 = f.read() + job_6_expected_input_file = """***,HNO_t +memory,Total=438,m; + +geometry={angstrom; +N -0.08142000 0.37454000 0.00000000 +O 1.01258000 -0.17285000 0.00000000 +H -0.93116000 -0.20169000 0.00000000} + +gprint,orbitals; + +basis=aug-cc-pvtz + + + +int; + +{hf; + maxit,999; + wf,spin=0,charge=0; +} + + +{mp2; + wf,spin=0,charge=0; +} + +{casscf; + maxit,999; + wf,spin=0,charge=0; +} + +{rs2c; + maxit,999; + wf,spin=0,charge=0; +} + + + + +---; + +""" + self.assertEqual(content_6, job_6_expected_input_file) + + self.job_7.cpu_cores = 48 + self.job_7.set_input_file_memory() + self.job_7.write_input_file() + with open(os.path.join(self.job_7.local_path, input_filenames[self.job_7.job_adapter]), 'r') as f: + content_7 = f.read() + job_7_expected_input_file = """***,N +memory,Total=438,m; + +geometry={angstrom; +N 0.00000000 0.00000000 0.00000000} + +gprint,orbitals; + +basis=aug-cc-pvtz + + + +int; + +{hf; + maxit,999; + wf,spin=3,charge=0; +} + + +{mp2; + wf,spin=3,charge=0; +} + +{casscf; + maxit,999; + wf,spin=3,charge=0; + occ,3,1,1,0,1,0,0,0; + closed,1,0,0,0,0,0,0,0; + state,1; +} + +{rs2c; + maxit,999; + wf,spin=3,charge=0; +} + + + + +---; + +""" + self.assertEqual(content_7, job_7_expected_input_file) + def test_set_files(self): """Test setting files""" job_1_files_to_upload = [{'file_name': 'submit.sub', @@ -154,8 +463,8 @@ def tearDownClass(cls): A function that is run ONCE after all unit tests in this class. Delete all project directories created during these unit tests """ - for folder in ['test_MolproAdapter_1', 'test_MolproAdapter_2']: - shutil.rmtree(os.path.join(ARC_PATH, 'arc', 'testing', folder), ignore_errors=True) + for i in range(10): + shutil.rmtree(os.path.join(ARC_PATH, 'arc', 'testing', f'test_MolproAdapter_{i}'), ignore_errors=True) if __name__ == '__main__':