Working directory : /state/partition1/1195123/molpro.2u06cOEDfz/ Global scratch directory : /state/partition1/1195123/molpro.2u06cOEDfz/ Wavefunction directory : /home/boggio/wfu/ Main file repository : /state/partition1/1195123/molpro.2u06cOEDfz/ id : irsamc Nodes nprocs compute-14-4.local 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=df Variables initialized (1009), CPU time= 0.00 sec ***,pyrrole, CASPT3(6,5)/aug-cc-pVTZ 1A1 and triplet 1B2 calculation memory,2000,m file,2,pyrr_sa2cas5_avtz_3b2.wfu GEOMTYP=xyz BOHR GEOMETRY={ 10 CC3/aug-cc-pVTZ S0 optimised geometry C 0.00000000 2.11924634 0.62676569 C 0.00000000 -2.11924634 0.62676569 C 0.00000000 1.34568862 -1.85506908 C 0.00000000 -1.34568862 -1.85506908 N 0.00000000 0.00000000 2.10934391 H 0.00000000 0.00000000 4.00257355 H 0.00000000 3.97648410 1.44830201 H 0.00000000 -3.97648410 1.44830201 H 0.00000000 2.56726559 -3.47837232 H 0.00000000 -2.56726559 -3.47837232} BASIS=AVTZ INT {MULTI occ,9,3,6,2 closed,9,0,6,0 wf,36,1,0 wf,36,3,2 canonical print,orbitals,civector} {RS3,shift=0.3 wf,36,1,0} {RS3,shift=0.3 wf,36,3,2} {RS3,shift=0.3,ipea=0.25 wf,36,1,0} {RS3,shift=0.3,ipea=0.25 wf,36,3,2} Commands initialized (810), CPU time= 0.00 sec, 661 directives. Default parameters read. Elapsed time= 0.08 sec Checking input... Passed 1 *** PROGRAM SYSTEM MOLPRO *** Copyright, TTI GmbH Stuttgart, 2015 Version 2021.2 linked Jun 2 2021 16:00:59 ********************************************************************************************************************************** LABEL * pyrrole, CASPT3(6,5)/aug-cc-pVTZ 1A1 and triplet 1B2 calculation 64 bit serial version DATE: 13-Jan-22 TIME: 08:46:01 ********************************************************************************************************************************** SHA1: 1987c3f1b0c3ae76932bc24993909f2d7ae6b1f1 ********************************************************************************************************************************** Memory per process: 2000 MW Total memory per node: 2000 MW GA preallocation disabled GA check disabled Variable memory set to 2000.0 MW Permanent file 2 pyrr_sa2cas5_avtz_3b2.wfu assigned. Implementation=df Size= 20.24 MB PROGRAM * RESTART Reading variables from file 2 _AVOGAD = 0.60221367D+24 1/MOL _BOLTZ = 0.00000000 _EV = 0.03674932 _ENULL = 0.00000000 _KJOULE = 0.00038088 _KJOULE/MOL = 0.00038088 _CM = 0.00000456 _CM-1 = 0.00000456 _DEB2SI = 0.00000000 _AMU2AU = 1822.88839000 _KCAL = 0.00159360 _KCAL/MOL = 0.00159360 _KELVIN = 0.00000317 _JOULE = 0.00000000 _HERTZ = 0.00000000 _HZ = 0.00000000 _PLANCK = 0.00000000 _TOA = 0.52917721 _TOANG = 0.52917721 _TOCM = 0.21947463D+06 CM-1 _TODEBYE = 2.54158000 _TOE = 0.00000000 _TOEV = 27.21138505 _TOHERTZ = 0.65796839D+16 HZ _TOHZ = 0.65796839D+16 HZ _TOK = 0.31577504D+06 K _TOKCAL = 627.50960000 _TOKELVIN = 0.31577504D+06 K _TOKJ = 2625.50000000 _TOKJOULE = 2625.50000000 _TOKG = 0.00000000 _ANG = 1.88972612 _ANGSTROM = 1.88972612 _FNUC = 0.00000000 _BASIS = AVTZ _ZUNIT = BOHR _NELEC = 36.00000000 _PROGRAM = MULTI _DMX(2) = 0.00000000 _DMY(2) = 0.00000000 _DMZ(1:2) = 0.69058651 0.31953307 _DMX_SCF = 0.00000000 _DMY_SCF = 0.00000000 _DMZ_SCF = 0.77875663 _HOMO = 1.40000000 _EHOMO = -0.29290281 _LUMO = 10.10000000 _ELUMO = 0.17903199 _ENERGY(1:2) = -208.93149678 -208.77560053 _ENERGY_METHOD = MULTI _ENERGY_BASIS = aug-cc-pVTZ _ENUC = 161.27557595 _IPROC_MPP = 0.00000000 _IPROC_MPPX = 0.00000000 _ORBITAL = 2141.20000000 _STATUS = 1.00000000 _VERSION = 0.20190010D+07 _DATE = 15-Oct-19 _LASTORB = MCSCF _MACHINE = 64 bit serial version _OUTPUT = /home/boggio/PYRROLE/molpro.xml _PGROUP = C2v _TIME = 16:43:33 _LIBMOL = /home/thierry/PROGRAMS/Molpro2018/Molpro_release/lib/ _DMX_CC(1:2) = -0.00000000 -0.00000000 _DMY_CC(1:2) = -0.00000000 -0.00000000 _DMZ_CC(1:2) = 1.60215840 1.60215840 _DMX_NUC(1:2) = 0.00000000 0.00000000 _DMY_NUC(1:2) = 0.00000000 0.00000000 _DMZ_NUC(1:2) = -0.03180038 -0.03180038 _TRDMX = -0.00000000 _TRDMY = -0.00000000 _TRDMZ = -0.00000000 Geometry written to block 1 of record 700 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 2 9 20.24 500 610 700 1000 520 2100 2140 1001 2141 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF PROGRAMS * TOTAL RESTART CPU TIMES * 0.12 0.01 REAL TIME * 0.35 SEC DISK USED * 31.72 MB ********************************************************************************************************************************** SETTING GEOMTYP = XYZ ZUNIT=BOHR SETTING BASIS = AVTZ Using spherical harmonics Library entry C S aug-cc-pVTZ selected for orbital group 1 Library entry C P aug-cc-pVTZ selected for orbital group 1 Library entry C D aug-cc-pVTZ selected for orbital group 1 Library entry C F aug-cc-pVTZ selected for orbital group 1 Library entry N S aug-cc-pVTZ selected for orbital group 2 Library entry N P aug-cc-pVTZ selected for orbital group 2 Library entry N D aug-cc-pVTZ selected for orbital group 2 Library entry N F aug-cc-pVTZ selected for orbital group 2 Library entry H S aug-cc-pVTZ selected for orbital group 3 Library entry H P aug-cc-pVTZ selected for orbital group 3 Library entry H D aug-cc-pVTZ 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 C2v ATOMIC COORDINATES NR ATOM CHARGE X Y Z 1 C 6.00 0.000000000 2.119246340 0.626765690 2 C 6.00 0.000000000 -2.119246340 0.626765690 3 C 6.00 0.000000000 1.345688620 -1.855069080 4 C 6.00 0.000000000 -1.345688620 -1.855069080 5 N 7.00 0.000000000 0.000000000 2.109343910 6 H 1.00 0.000000000 0.000000000 4.002573550 7 H 1.00 0.000000000 3.976484100 1.448302010 8 H 1.00 0.000000000 -3.976484100 1.448302010 9 H 1.00 0.000000000 2.567265590 -3.478372320 10 H 1.00 0.000000000 -2.567265590 -3.478372320 Bond lengths in Bohr (Angstrom) 1-3 2.599595232 1-5 2.586357135 1-7 2.030825946 2-4 2.599595232 2-5 2.586357135 ( 1.375646555) ( 1.368641255) ( 1.074666810) ( 1.375646555) ( 1.368641255) 2- 8 2.030825946 3- 4 2.691377240 3- 9 2.031591421 4-10 2.031591421 5- 6 1.893229640 ( 1.074666810) ( 1.424215501) ( 1.075071882) ( 1.075071882) ( 1.001853981) Bond angles 1-3-4 107.31162150 1-3-9 125.72598728 1-5-2 110.04841705 1-5-6 124.97579147 2- 4- 3 107.31162150 2- 4-10 125.72598728 2- 5- 6 124.97579147 3- 1- 5 107.66416997 3- 1- 7 131.17349374 3- 4-10 126.96239122 4- 2- 5 107.66416997 4- 2- 8 131.17349374 4-3-9 126.96239122 5-1-7 121.16233629 5-2-8 121.16233629 NUCLEAR CHARGE: 36 NUMBER OF PRIMITIVE AOS: 470 NUMBER OF SYMMETRY AOS: 415 NUMBER OF CONTRACTIONS: 345 ( 122A1 + 62B1 + 108B2 + 53A2 ) NUMBER OF INNER CORE ORBITALS: 0 ( 0A1 + 0B1 + 0B2 + 0A2 ) NUMBER OF OUTER CORE ORBITALS: 5 ( 3A1 + 0B1 + 2B2 + 0A2 ) NUMBER OF VALENCE ORBITALS: 25 ( 11A1 + 3B1 + 9B2 + 2A2 ) NUCLEAR REPULSION ENERGY 161.27557595 Eigenvalues of metric 1 0.131E-04 0.207E-04 0.378E-04 0.505E-04 0.645E-04 0.851E-04 0.123E-03 0.295E-03 2 0.943E-03 0.273E-02 0.280E-02 0.402E-02 0.529E-02 0.691E-02 0.910E-02 0.109E-01 3 0.361E-05 0.510E-05 0.813E-05 0.121E-04 0.210E-04 0.432E-04 0.778E-04 0.106E-03 4 0.236E-03 0.188E-02 0.213E-02 0.254E-02 0.320E-02 0.366E-02 0.473E-02 0.754E-02 Contracted 2-electron integrals neglected if value below 1.0D-12 AO integral compression algorithm 1 Integral accuracy 1.0D-12 2605.711 MB (compressed) written to integral file ( 60.8%) NUMBER OF SORTED TWO-ELECTRON INTEGRALS: 455095713. BUFFER LENGTH: 32768 NUMBER OF SEGMENTS: 15 SEGMENT LENGTH: 31999644 RECORD LENGTH: 524288 Memory used in sort: 32.56 MW SORT1 READ 536132112. AND WROTE 449114045. INTEGRALS IN 1295 RECORDS. CPU TIME: 8.69 SEC, REAL TIME: 11.55 SEC SORT2 READ 449114045. AND WROTE 455095713. INTEGRALS IN 9940 RECORDS. CPU TIME: 5.05 SEC, REAL TIME: 6.49 SEC FILE SIZES: FILE 1: 2638.5 MBYTE, FILE 4: 5431.7 MBYTE, TOTAL: 8070.1 MBYTE OPERATOR DM FOR CENTER 0 COORDINATES: 0.000000 0.000000 0.000000 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 19 2236.16 500 700 610 900 950 970 1001 129 960 1100 VAR GEOM BASINP SYMINP ZMAT AOBASIS BASIS P2S ABASIS S 1400 1410 1200 1210 1080 1600 1650 1300 1700 T V H0 H01 AOSYM SMH MOLCAS ERIS OPER 2 9 20.24 500 610 700 1000 520 2100 2140 1001 2141 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF PROGRAMS * TOTAL INT RESTART CPU TIMES * 37.87 37.75 0.01 REAL TIME * 44.59 SEC DISK USED * 7.54 GB ********************************************************************************************************************************** PROGRAM * MULTI (Direct Multiconfiguration SCF) Authors: P.J. Knowles, H.-J. Werner (1984) D.A. Kreplin, P.J. Knowles, H.-J. Werner (2019) Number of closed-shell orbitals: 15 ( 9 0 6 0 ) Number of active orbitals: 5 ( 0 3 0 2 ) Number of external orbitals: 325 ( 113 59 102 51 ) State symmetry 1 Number of active electrons: 6 Spin symmetry=Singlet Space symmetry=1 Number of states: 1 Number of CSFs: 28 (52 determinants, 100 intermediate states) State symmetry 2 Number of active electrons: 6 Spin symmetry=Triplet Space symmetry=3 Number of states: 1 Number of CSFs: 24 (26 determinants, 50 intermediate states) Molecular orbitals read from record 2141.2 Type=MCSCF/NATURAL (state averaged) Wavefunction dump at record 2141.2 Convergence thresholds 0.10E-04 (gradient) 0.10E-05 (energy) Weight factors for state symmetry 1: 0.50000 Weight factors for state symmetry 2: 0.50000 Number of orbital rotations: 1908 ( 0 closed/active, 1629 closed/virtual, 0 active/active, 279 active/virtual ) Total number of variables: 1986 Second-order MCSCF: L-BFGS accelerated ITER MIC NCI NEG ENERGY(VAR) ENERGY(PROJ) ENERGY CHANGE GRAD(0) GRAD(ORB) GRAD(CI) STEP TIME 1 4 4 0 -208.85354865 -208.85354865 -0.00000000 0.00000002 0.00000000 0.00000000 0.11E-07 4.51 CONVERGENCE REACHED! Final gradient: 0.00000000 ( 0.84E-09) Final energy: -208.85354865 Molecular orbital coefficients: Orbital Occupation Energy Cen Mu Typ Coefficients 1.1 2.00000 0.00000 5 1 s 0.99930 2.1 2.00000 0.00000 1 1 s 1.00033 3.1 2.00000 0.00000 3 1 s 1.00052 4.1 2.00000 0.00000 1 2 s 0.48815 3 2 s 0.27182 3 4 s -0.43454 5 2 s 0.67988 5.1 2.00000 0.00000 1 1 pz -0.29177 3 2 s 0.73164 5 2 s -0.42361 6 1 s -0.28894 6.1 2.00000 0.00000 1 2 s 0.44981 3 2 s -0.38022 3 1 pz 0.35326 5 1 pz -0.42436 6 1 s -0.50049 9 1 s -0.35452 7.1 2.00000 0.00000 1 2 s 0.34769 1 1 py 0.51964 3 1 py 0.30690 5 1 pz 0.28820 7 1 s 0.62417 7 3 s -0.27549 8.1 2.00000 0.00000 1 1 pz -0.42331 3 1 pz 0.55579 5 1 pz 0.45349 6 1 s 0.45187 9 1 s -0.53018 9.1 2.00000 0.00000 1 1 pz -0.40330 3 1 py 0.79025 7 1 s -0.42437 9 1 s 0.35782 1.2 1.00000 0.00000 1 1 px 0.35487 5 1 px 0.77889 2.2 1.00000 0.00000 1 1 px 0.28984 3 1 px 0.75496 3.2 1.00000 0.00000 1 1 px 0.84475 3 1 px -0.41047 5 1 px -0.44640 1.3 2.00000 0.00000 1 1 s 1.00063 2.3 2.00000 0.00000 3 1 s 1.00012 3.3 2.00000 0.00000 1 2 s 0.77564 3 2 s 0.42061 5 1 py 0.28100 7 1 s 0.31431 7 3 s -0.26947 4.3 2.00000 0.00000 1 4 s 0.40224 1 1 pz 0.46123 3 2 s -0.56668 3 1 py -0.26114 5 1 py 0.38020 9 1 s -0.46746 9 3 s 0.34517 5.3 2.00000 0.00000 1 1 py 0.68278 5 1 py -0.47090 7 1 s 0.70045 7 3 s -0.43879 6.3 2.00000 0.00000 1 4 s -0.25027 1 1 pz -0.51725 3 4 s -0.29220 3 5 s -0.33375 3 1 pz 0.64588 9 1 s -0.66506 9 3 s 0.35468 1.4 1.00000 0.00000 1 1 px 0.78100 3 1 px 0.43506 2.4 1.00000 0.00000 1 1 px -0.60518 3 1 px 1.05779 3 3 px 0.26387 CI Coefficients of symmetry 1 ============================= 220 20 0.96269320 222 00 -0.15228798 200 22 -0.10002885 2ab ba -0.08952857 2ba ab -0.08952857 220 02 -0.06655482 Energy: -208.93149677 CI Coefficients of symmetry 3 ============================= 22a a0 0.93904434 2a0 2a 0.25519054 20a a2 -0.13033165 2a2 0a -0.09072502 20a 2a 0.08976408 2a2 a0 0.08133620 22a 0a -0.07890130 2a0 a2 -0.06798266 Energy: -208.77560053 Results for state 1.1 ===================== !MCSCF STATE 1.1 Energy -208.931496774783 Nuclear energy 161.27557595 Kinetic energy 208.69825809 One electron energy -601.33252079 Two electron energy 231.12544806 Virial ratio 2.00111759 !MCSCF STATE 1.1 Dipole moment 0.00000000 0.00000000 0.69058650 Dipole moment /Debye 0.00000000 0.00000000 1.75518085 Results for state 1.3 ===================== !MCSCF STATE 1.3 Energy -208.775600532205 Nuclear energy 161.27557595 Kinetic energy 209.14659406 One electron energy -601.14466226 Two electron energy 231.09348578 Virial ratio 1.99822616 !MCSCF STATE 1.3 Dipole moment 0.00000000 0.00000000 0.31953307 Dipole moment /Debye 0.00000000 0.00000000 0.81211887 State-averaged charge density matrix saved on record 2141.2 (density set 1) Expectation values: (only non-zero values are shown) !MCSCF expec <1.1|DMZ|1.1> 0.690586503374 au = 1.755180845245 Debye !MCSCF expec <1.3|DMZ|1.3> 0.319533073891 au = 0.812118869940 Debye PSEUDO CANONICAL ORBITALS (STATE AVERAGED) ========================================== Orbital Occupation Energy Cen Mu Typ Coefficients 1.1 2.00000 -15.57035 5 1 s 0.99930 2.1 2.00000 -11.23640 1 1 s 1.00033 3.1 2.00000 -11.20842 3 1 s 1.00052 4.1 2.00000 -1.27895 1 2 s 0.48815 3 2 s 0.27182 3 4 s -0.43454 5 2 s 0.67988 5.1 2.00000 -1.03726 1 1 pz -0.29177 3 2 s 0.73164 5 2 s -0.42361 6 1 s -0.28894 6.1 2.00000 -0.78404 1 2 s 0.44981 3 2 s -0.38022 3 1 pz 0.35326 5 1 pz -0.42436 6 1 s -0.50049 9 1 s -0.35452 7.1 2.00000 -0.73040 1 2 s 0.34769 1 1 py 0.51964 3 1 py 0.30690 5 1 pz 0.28820 7 1 s 0.62417 7 3 s -0.27549 8.1 2.00000 -0.58677 1 1 pz -0.42331 3 1 pz 0.55579 5 1 pz 0.45349 6 1 s 0.45187 9 1 s -0.53018 9.1 2.00000 -0.52735 1 1 pz -0.40330 3 1 py 0.79025 7 1 s -0.42437 9 1 s 0.35782 1.2 1.97865 -0.55125 1 1 px 0.45456 3 1 px 0.30173 5 1 px 0.61371 2.2 1.92180 -0.33897 3 1 px 0.69417 5 1 px -0.51039 3.2 0.51569 0.12963 1 1 px 0.84027 3 1 px -0.40707 5 1 px -0.45942 1.3 2.00000 -11.23643 1 1 s 1.00063 2.3 2.00000 -11.20737 3 1 s 1.00012 3.3 2.00000 -0.97060 1 2 s 0.77564 3 2 s 0.42061 5 1 py 0.28100 7 1 s 0.31431 7 3 s -0.26947 4.3 2.00000 -0.76314 1 4 s 0.40224 1 1 pz 0.46123 3 2 s -0.56668 3 1 py -0.26114 5 1 py 0.38020 9 1 s -0.46746 9 3 s 0.34517 5.3 2.00000 -0.57280 1 1 py 0.68278 5 1 py -0.47090 7 1 s 0.70045 7 3 s -0.43879 6.3 2.00000 -0.54847 1 4 s -0.25027 1 1 pz -0.51725 3 4 s -0.29220 3 5 s -0.33375 3 1 pz 0.64588 9 1 s -0.66506 9 3 s 0.35468 1.4 1.48698 -0.23166 1 1 px 0.77230 3 1 px 0.45009 2.4 0.09688 0.28285 1 1 px -0.61625 3 1 px 1.05148 3 3 px 0.26347 Canonical orbital dump (state averaged) at molpro section 2141.2 (Orbital set 2) Reoptimze the CI vectors with pseudo canonical orbitals CI Coefficients of symmetry 1 ============================= 220 20 0.96310185 222 00 -0.15228798 200 22 -0.08505260 2ab ba -0.07848017 2ba ab -0.07848017 220 02 -0.06708568 202 20 -0.05638046 2ba ba 0.05389207 2ab ab 0.05389207 Energy: -208.93149677 CI Coefficients of symmetry 3 ============================= 22a a0 0.93786116 2a0 2a 0.22171363 a20 2a 0.12854771 20a a2 -0.11274804 22a 0a -0.09258721 20a 2a 0.08682941 2a2 0a -0.08077305 2a0 a2 -0.06686717 2a2 a0 0.05816792 a22 a0 0.05544642 Energy: -208.77560053 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 2310.61 500 700 610 900 950 970 1001 129 960 1100 VAR GEOM BASINP SYMINP ZMAT AOBASIS BASIS P2S ABASIS S 1400 1410 1200 1210 1080 1600 1650 1300 1700 1380 T V H0 H01 AOSYM SMH MOLCAS ERIS OPER JKOP 2 9 20.24 500 610 700 1000 520 2100 2140 1001 2141 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF PROGRAMS * TOTAL MULTI INT RESTART CPU TIMES * 46.08 8.21 37.75 0.01 REAL TIME * 53.49 SEC DISK USED * 7.54 GB ********************************************************************************************************************************** PROGRAM * CI (Multireference internally contracted CI) Authors: H.-J. Werner, P.J. Knowles, 1987 PROGRAM * RS3 (Multireference RS Perturbation Theory) Authors: H.-J. Werner (1993), P. Celani (1998) Level shift= 0.30 Convergence thresholds: THRVAR = 1.00D-08 THRDEN = 1.00D-06 Number of optimized states: 1 Roots: 1 Number of reference states: 1 Roots: 1 Reference symmetry: 1 Singlet Number of electrons: 36 Maximum number of shells: 5 Maximum number of spin couplings: 14 Reference space: 25 conf 28 CSFs N elec internal: 1170 conf 1725 CSFs N-1 el internal: 2151 conf 5475 CSFs N-2 el internal: 1930 conf 7815 CSFs Number of electrons in valence space: 26 Maximum number of open shell orbitals in reference space: 4 Maximum number of open shell orbitals in internal spaces: 8 Number of core orbitals: 5 ( 3 0 2 0 ) Number of closed-shell orbitals: 10 ( 6 0 4 0 ) Number of active orbitals: 5 ( 0 3 0 2 ) Number of external orbitals: 325 ( 113 59 102 51 ) Molecular orbitals read from record 2141.2 Type=MCSCF/CANONICAL (state averaged) Integral transformation finished. Total CPU: 3.44 sec, npass= 1 Memory used: 4.06 MW Number of p-space configurations: 4 Reference wavefunction optimized for reference space (refopt=1) State Reference Energy 1 -208.93149677 Number of blocks in overlap matrix: 8 Smallest eigenvalue: 0.31D-02 Number of N-2 electron functions: 225 Number of N-1 electron functions: 5475 Number of internal configurations: 679 Number of singly external configurations: 351069 Number of doubly external configurations: 3008001 Total number of contracted configurations: 3359749 Total number of uncontracted configurations: 109445356 Weight factors for SA-density in H0: 1.000000 FIMAX= 0.13D-01 FXMAX= 0.17D-01 DIAG= F F NOREF=1 NOINT=0 IHPPD=2 Nuclear energy: 161.27557595 Core energy: -251.70869285 Zeroth-order valence energy: -17.88982671 Zeroth-order total energy: -108.32294360 First-order energy: -100.60855317 Diagonal Coupling coefficients finished. Storage: 634340 words, CPU-Time: 0.01 seconds. Energy denominators for pairs finished in 0 passes. Storage: 315097 words, CPU-time: 0.01 seconds. A level shift of 0.30 is applied. ITER. STATE ROOT SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) TIME 1 1 1 1.04565975 -0.01369792 -208.94519470 -0.01369792 -0.74806744 0.46D-01 0.16D+00 5.06 2 1 1 1.20406847 -0.80866041 -209.74015718 -0.79496249 0.00102366 0.64D-04 0.13D-03 5.48 3 1 1 1.20351248 -0.80896544 -209.74046222 -0.00030503 -0.00033885 0.86D-06 0.19D-06 5.92 4 1 1 1.20358801 -0.80899026 -209.74048704 -0.00002482 0.00000580 0.17D-08 0.47D-08 6.35 5 1 1 1.20358703 -0.80898997 -209.74048674 0.00000029 -0.00000170 0.54D-10 0.11D-10 6.77 6 1 1 1.20358729 -0.80899004 -209.74048682 -0.00000008 0.00000004 0.17D-12 0.41D-12 7.19 Energies without level shift correction: 6 1 1 1.20358729 -0.74791386 -209.67941063 Energy contributions for state 1.1: =================================== Energy contr. SQ.Norm of FOWF Space I -0.00194611 0.00087135 Space S -0.10962415 0.04470092 Space P -0.63634359 0.15801502 ===================================== Analysis of CPU times by interactions ===================================== I S P I 0.4% S 1.9% 1.3% P 0.3% 19.1% 5.1% Initialization: 69.3% Other: 2.6% Total CPU: 7.2 seconds ===================================== gnormi= 1.00087135 gnorms= 0.04470092 gnormp= 0.15801502 gnorm= 1.20358729 ecorri= -0.00194611 ecorrs= -0.10962415 ecorrp= -0.63634359 ecorr= -0.80899004 Reference coefficients greater than 0.0500000 ============================================= 222222220222220 0.9631018 222222222222200 -0.1522881 2222222/\2222/\ 0.1323721 222222200222222 -0.0850523 222222/2/2222\\ 0.0750343 222222220222202 -0.0670854 222222202222220 -0.0563805 RESULTS FOR STATE 1.1 ===================== Coefficient of reference function: C(0) = 1.00000000 (fixed) 1.00000000 (relaxed) Energy contributions of configuration classes CLASS SQ.NORM ECORR1 ECORR2 +++++++++++++++++++++++++++++++++++++++++++++++++++ Internals 0.00087135 -0.00194611 0.80477995 Singles 0.04470092 -0.10962415 -0.23715256 Pairs 0.15801502 -0.63634358 -1.37661743 Total 1.20358729 -0.74791383 -0.80899004 +++++++++++++++++++++++++++++++++++++++++++++++++++ Reference energy -208.93149677 Nuclear energy 161.27557595 Kinetic energy 209.19875233 One electron energy -600.89094224 Two electron energy 229.87487947 Virial quotient -1.00258957 Correlation energy -0.80899004 !RSPT2 STATE 1.1 Energy -209.740486817418 Properties without orbital relaxation: !RSPT2 STATE 1.1 Dipole moment 0.00000000 0.00000000 0.66348363 Dipole moment /Debye 0.00000000 0.00000000 1.68629671 !RSPT expec <1.1|H|1.1> -209.619048782406 Correlation energy -0.82752885 !RSPT3 STATE 1.1 Energy -209.759025622577 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 2310.61 500 700 610 900 950 970 1001 129 960 1100 VAR GEOM BASINP SYMINP ZMAT AOBASIS BASIS P2S ABASIS S 1400 1410 1200 1210 1080 1600 1650 1300 1700 1380 T V H0 H01 AOSYM SMH MOLCAS ERIS OPER JKOP 2 9 20.24 500 610 700 1000 520 2100 2140 1001 2141 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF PROGRAMS * TOTAL RS3 MULTI INT RESTART CPU TIMES * 68.53 22.45 8.21 37.75 0.01 REAL TIME * 77.20 SEC DISK USED * 7.54 GB ********************************************************************************************************************************** PROGRAM * CI (Multireference internally contracted CI) Authors: H.-J. Werner, P.J. Knowles, 1987 PROGRAM * RS3 (Multireference RS Perturbation Theory) Authors: H.-J. Werner (1993), P. Celani (1998) Level shift= 0.30 Convergence thresholds: THRVAR = 1.00D-08 THRDEN = 1.00D-06 Number of optimized states: 1 Roots: 1 Number of reference states: 1 Roots: 1 Reference symmetry: 3 Triplet Number of electrons: 36 Maximum number of shells: 4 Maximum number of spin couplings: 28 Reference space: 20 conf 24 CSFs N elec internal: 1110 conf 2220 CSFs N-1 el internal: 2151 conf 8799 CSFs N-2 el internal: 1624 conf 13564 CSFs Number of electrons in valence space: 26 Maximum number of open shell orbitals in reference space: 4 Maximum number of open shell orbitals in internal spaces: 8 Number of core orbitals: 5 ( 3 0 2 0 ) Number of closed-shell orbitals: 10 ( 6 0 4 0 ) Number of active orbitals: 5 ( 0 3 0 2 ) Number of external orbitals: 325 ( 113 59 102 51 ) Molecular orbitals read from record 2141.2 Type=MCSCF/CANONICAL (state averaged) Coulomb and exchange operators available. No transformation done. Number of p-space configurations: 7 Reference wavefunction optimized for reference space (refopt=1) State Reference Energy 1 -208.77560053 Number of blocks in overlap matrix: 8 Smallest eigenvalue: 0.20D-02 Number of N-2 electron functions: 225 Number of N-1 electron functions: 8799 Number of internal configurations: 870 Number of singly external configurations: 560055 Number of doubly external configurations: 3008001 Total number of contracted configurations: 3568926 Total number of uncontracted configurations: 190082977 Weight factors for SA-density in H0: 1.000000 FIMAX= 0.13D-01 FXMAX= 0.17D-01 DIAG= F F NOREF=1 NOINT=0 IHPPD=2 Nuclear energy: 161.27557595 Core energy: -251.70869285 Zeroth-order valence energy: -17.38877373 Zeroth-order total energy: -107.82189063 First-order energy: -100.95370990 Diagonal Coupling coefficients finished. Storage: 647816 words, CPU-Time: 0.01 seconds. Energy denominators for pairs finished in 0 passes. Storage: 321222 words, CPU-time: 0.00 seconds. A level shift of 0.30 is applied. ITER. STATE ROOT SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) TIME 1 1 1 1.04381680 -0.01314504 -208.78874557 -0.01314504 -0.74466975 0.44D-01 0.16D+00 0.21 2 1 1 1.20778586 -0.80662567 -209.58222620 -0.79348063 0.00052825 0.65D-04 0.92D-04 0.80 3 1 1 1.20741567 -0.80686657 -209.58246711 -0.00024091 -0.00023335 0.75D-06 0.22D-06 1.40 4 1 1 1.20749359 -0.80689165 -209.58249218 -0.00002508 0.00000249 0.33D-08 0.43D-08 2.00 5 1 1 1.20749347 -0.80689162 -209.58249215 0.00000004 -0.00000125 0.76D-10 0.26D-10 2.60 Energies without level shift correction: 5 1 1 1.20749347 -0.74464358 -209.52024411 Energy contributions for state 1.3: =================================== Energy contr. SQ.Norm of FOWF Space I -0.00159057 0.00076156 Space S -0.09650107 0.04339322 Space P -0.64655193 0.16333868 ===================================== Analysis of CPU times by interactions ===================================== I S P I 1.2% S 6.5% 6.5% P 1.2% 63.1% 11.9% Initialization: 4.6% Other: 5.0% Total CPU: 2.6 seconds ===================================== gnormi= 1.00076156 gnorms= 0.04339322 gnormp= 0.16333868 gnorm= 1.20749347 ecorri= -0.00159057 ecorrs= -0.09650107 ecorrp= -0.64655193 ecorr= -0.80689162 Reference coefficients greater than 0.0500000 ============================================= 22222222/2222/0 0.9378611 2222222/022222/ 0.2217138 222222/2022222/ 0.1285476 22222220/2222/2 -0.1127480 22222222/22220/ -0.0925871 22222220/22222/ 0.0868294 2222222/222220/ -0.0807734 2222222/02222/2 -0.0668671 222222/\/2222/2 0.0592853 2222222/22222/0 0.0581679 222222/222222/0 0.0554463 RESULTS FOR STATE 1.3 ===================== Coefficient of reference function: C(0) = 1.00000000 (fixed) 1.00000000 (relaxed) Energy contributions of configuration classes CLASS SQ.NORM ECORR1 ECORR2 +++++++++++++++++++++++++++++++++++++++++++++++++++ Internals 0.00076156 -0.00159057 0.80344457 Singles 0.04339322 -0.09650108 -0.20913606 Pairs 0.16333868 -0.64655194 -1.40120012 Total 1.20749347 -0.74464359 -0.80689162 +++++++++++++++++++++++++++++++++++++++++++++++++++ Reference energy -208.77560053 Nuclear energy 161.27557595 Kinetic energy 209.60595704 One electron energy -600.73670931 Two electron energy 229.87864121 Virial quotient -0.99988805 Correlation energy -0.80689162 !RSPT2 STATE 1.3 Energy -209.582492148635 Properties without orbital relaxation: !RSPT2 STATE 1.3 Dipole moment 0.00000000 0.00000000 0.36076546 Dipole moment /Debye 0.00000000 0.00000000 0.91691429 !RSPT expec <1.3|H|1.3> -209.454966600440 Correlation energy -0.82033034 !RSPT3 STATE 1.3 Energy -209.595930873888 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 2310.61 500 700 610 900 950 970 1001 129 960 1100 VAR GEOM BASINP SYMINP ZMAT AOBASIS BASIS P2S ABASIS S 1400 1410 1200 1210 1080 1600 1650 1300 1700 1380 T V H0 H01 AOSYM SMH MOLCAS ERIS OPER JKOP 2 9 20.24 500 610 700 1000 520 2100 2140 1001 2141 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF PROGRAMS * TOTAL RS3 RS3 MULTI INT RESTART CPU TIMES * 88.54 20.01 22.45 8.21 37.75 0.01 REAL TIME * 98.03 SEC DISK USED * 7.54 GB ********************************************************************************************************************************** PROGRAM * CI (Multireference internally contracted CI) Authors: H.-J. Werner, P.J. Knowles, 1987 PROGRAM * RS3 (Multireference RS Perturbation Theory) Authors: H.-J. Werner (1993), P. Celani (1998) IPEA shift= 0.25 Level shift= 0.30 Convergence thresholds: THRVAR = 1.00D-08 THRDEN = 1.00D-06 Number of optimized states: 1 Roots: 1 Number of reference states: 1 Roots: 1 Reference symmetry: 1 Singlet Number of electrons: 36 Maximum number of shells: 5 Maximum number of spin couplings: 14 Reference space: 25 conf 28 CSFs N elec internal: 1170 conf 1725 CSFs N-1 el internal: 2151 conf 5475 CSFs N-2 el internal: 1930 conf 7815 CSFs Number of electrons in valence space: 26 Maximum number of open shell orbitals in reference space: 4 Maximum number of open shell orbitals in internal spaces: 8 Number of core orbitals: 5 ( 3 0 2 0 ) Number of closed-shell orbitals: 10 ( 6 0 4 0 ) Number of active orbitals: 5 ( 0 3 0 2 ) Number of external orbitals: 325 ( 113 59 102 51 ) Molecular orbitals read from record 2141.2 Type=MCSCF/CANONICAL (state averaged) Coulomb and exchange operators available. No transformation done. Number of p-space configurations: 4 Reference wavefunction optimized for reference space (refopt=1) State Reference Energy 1 -208.93149677 Number of blocks in overlap matrix: 8 Smallest eigenvalue: 0.31D-02 Number of N-2 electron functions: 225 Number of N-1 electron functions: 5475 Number of internal configurations: 679 Number of singly external configurations: 351069 Number of doubly external configurations: 3008001 Total number of contracted configurations: 3359749 Total number of uncontracted configurations: 109445356 Weight factors for SA-density in H0: 1.000000 FIMAX= 0.13D-01 FXMAX= 0.17D-01 DIAG= F F NOREF=1 NOINT=0 IHPPD=2 Nuclear energy: 161.27557595 Core energy: -251.70869285 Zeroth-order valence energy: -11.45973351 Zeroth-order total energy: -101.89285041 First-order energy: -107.03864637 Diagonal Coupling coefficients finished. Storage: 634340 words, CPU-Time: 0.01 seconds. Energy denominators for pairs finished in 0 passes. Storage: 315097 words, CPU-time: 0.00 seconds. A level shift of 0.30 is applied. ITER. STATE ROOT SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) TIME 1 1 1 1.04375319 -0.01312596 -208.94462273 -0.01312596 -0.74524148 0.44D-01 0.16D+00 0.21 2 1 1 1.20157133 -0.80519502 -209.73669179 -0.79206906 0.00096418 0.54D-04 0.12D-03 0.64 3 1 1 1.20105007 -0.80548800 -209.73698477 -0.00029298 -0.00032356 0.77D-06 0.17D-06 1.07 4 1 1 1.20112056 -0.80551115 -209.73700792 -0.00002315 0.00000530 0.15D-08 0.41D-08 1.51 5 1 1 1.20111970 -0.80551089 -209.73700766 0.00000026 -0.00000157 0.44D-10 0.10D-10 1.93 6 1 1 1.20111994 -0.80551096 -209.73700773 -0.00000007 0.00000003 0.14D-12 0.33D-12 2.36 Energies without level shift correction: 6 1 1 1.20111994 -0.74517497 -209.67667175 Energy contributions for state 1.1: =================================== Energy contr. SQ.Norm of FOWF Space I -0.00191173 0.00083817 Space S -0.10780710 0.04291680 Space P -0.63545615 0.15736498 ===================================== Analysis of CPU times by interactions ===================================== I S P I 1.3% S 5.1% 4.2% P 0.8% 59.3% 16.5% Initialization: 5.5% Other: 7.2% Total CPU: 2.4 seconds ===================================== gnormi= 1.00083817 gnorms= 0.04291680 gnormp= 0.15736498 gnorm= 1.20111994 ecorri= -0.00191173 ecorrs= -0.10780710 ecorrp= -0.63545615 ecorr= -0.80551096 Reference coefficients greater than 0.0500000 ============================================= 222222220222220 0.9631018 222222222222200 -0.1522881 2222222/\2222/\ 0.1323721 222222200222222 -0.0850523 222222/2/2222\\ 0.0750343 222222220222202 -0.0670854 222222202222220 -0.0563805 RESULTS FOR STATE 1.1 ===================== Coefficient of reference function: C(0) = 1.00000000 (fixed) 1.00000000 (relaxed) Energy contributions of configuration classes CLASS SQ.NORM ECORR1 ECORR2 +++++++++++++++++++++++++++++++++++++++++++++++++++ Internals 0.00083817 -0.00191173 0.80137789 Singles 0.04291680 -0.10780710 -0.23307223 Pairs 0.15736498 -0.63545613 -1.37381662 Total 1.20111994 -0.74517495 -0.80551096 +++++++++++++++++++++++++++++++++++++++++++++++++++ Reference energy -208.93149677 Nuclear energy 161.27557595 Kinetic energy 209.19810605 One electron energy -600.90552520 Two electron energy 229.89294152 Virial quotient -1.00257604 Correlation energy -0.80551096 !RSPT2 STATE 1.1 Energy -209.737007731031 Properties without orbital relaxation: !RSPT2 STATE 1.1 Dipole moment 0.00000000 0.00000000 0.66818505 Dipole moment /Debye 0.00000000 0.00000000 1.69824576 !RSPT expec <1.1|H|1.1> -209.620299560085 Correlation energy -0.82733475 !RSPT3 STATE 1.1 Energy -209.758831525825 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 2310.61 500 700 610 900 950 970 1001 129 960 1100 VAR GEOM BASINP SYMINP ZMAT AOBASIS BASIS P2S ABASIS S 1400 1410 1200 1210 1080 1600 1650 1300 1700 1380 T V H0 H01 AOSYM SMH MOLCAS ERIS OPER JKOP 2 9 20.24 500 610 700 1000 520 2100 2140 1001 2141 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF PROGRAMS * TOTAL RS3 RS3 RS3 MULTI INT RESTART CPU TIMES * 105.99 17.45 20.01 22.45 8.21 37.75 0.01 REAL TIME * 116.34 SEC DISK USED * 7.54 GB ********************************************************************************************************************************** PROGRAM * CI (Multireference internally contracted CI) Authors: H.-J. Werner, P.J. Knowles, 1987 PROGRAM * RS3 (Multireference RS Perturbation Theory) Authors: H.-J. Werner (1993), P. Celani (1998) IPEA shift= 0.25 Level shift= 0.30 Convergence thresholds: THRVAR = 1.00D-08 THRDEN = 1.00D-06 Number of optimized states: 1 Roots: 1 Number of reference states: 1 Roots: 1 Reference symmetry: 3 Triplet Number of electrons: 36 Maximum number of shells: 4 Maximum number of spin couplings: 28 Reference space: 20 conf 24 CSFs N elec internal: 1110 conf 2220 CSFs N-1 el internal: 2151 conf 8799 CSFs N-2 el internal: 1624 conf 13564 CSFs Number of electrons in valence space: 26 Maximum number of open shell orbitals in reference space: 4 Maximum number of open shell orbitals in internal spaces: 8 Number of core orbitals: 5 ( 3 0 2 0 ) Number of closed-shell orbitals: 10 ( 6 0 4 0 ) Number of active orbitals: 5 ( 0 3 0 2 ) Number of external orbitals: 325 ( 113 59 102 51 ) Molecular orbitals read from record 2141.2 Type=MCSCF/CANONICAL (state averaged) Coulomb and exchange operators available. No transformation done. Number of p-space configurations: 7 Reference wavefunction optimized for reference space (refopt=1) State Reference Energy 1 -208.77560053 Number of blocks in overlap matrix: 8 Smallest eigenvalue: 0.20D-02 Number of N-2 electron functions: 225 Number of N-1 electron functions: 8799 Number of internal configurations: 870 Number of singly external configurations: 560055 Number of doubly external configurations: 3008001 Total number of contracted configurations: 3568926 Total number of uncontracted configurations: 190082977 Weight factors for SA-density in H0: 1.000000 FIMAX= 0.13D-01 FXMAX= 0.17D-01 DIAG= F F NOREF=1 NOINT=0 IHPPD=2 Nuclear energy: 161.27557595 Core energy: -251.70869285 Zeroth-order valence energy: -11.20260522 Zeroth-order total energy: -101.63572212 First-order energy: -107.13987841 Diagonal Coupling coefficients finished. Storage: 647816 words, CPU-Time: 0.01 seconds. Energy denominators for pairs finished in 0 passes. Storage: 321222 words, CPU-time: 0.00 seconds. A level shift of 0.30 is applied. ITER. STATE ROOT SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) TIME 1 1 1 1.03710042 -0.01113012 -208.78673066 -0.01113012 -0.73438065 0.37D-01 0.16D+00 0.20 2 1 1 1.19789291 -0.79340980 -209.56901033 -0.78227968 0.00049722 0.45D-04 0.75D-04 0.80 3 1 1 1.19750743 -0.79359688 -209.56919741 -0.00018708 -0.00019875 0.46D-06 0.14D-06 1.40 4 1 1 1.19757077 -0.79361714 -209.56921768 -0.00002026 0.00000195 0.13D-08 0.23D-08 2.00 5 1 1 1.19757034 -0.79361701 -209.56921755 0.00000013 -0.00000092 0.26D-10 0.82D-11 2.59 6 1 1 1.19757058 -0.79361708 -209.56921761 -0.00000007 0.00000001 0.13D-12 0.19D-12 3.18 Energies without level shift correction: 6 1 1 1.19757058 -0.73434591 -209.50994644 Energy contributions for state 1.3: =================================== Energy contr. SQ.Norm of FOWF Space I -0.00149889 0.00067157 Space S -0.09058190 0.03671047 Space P -0.64226511 0.16018853 ===================================== Analysis of CPU times by interactions ===================================== I S P I 0.9% S 6.6% 6.6% P 0.6% 64.8% 11.9% Initialization: 3.8% Other: 4.7% Total CPU: 3.2 seconds ===================================== gnormi= 1.00067157 gnorms= 0.03671047 gnormp= 0.16018853 gnorm= 1.19757058 ecorri= -0.00149889 ecorrs= -0.09058190 ecorrp= -0.64226511 ecorr= -0.79361708 Reference coefficients greater than 0.0500000 ============================================= 22222222/2222/0 0.9378611 2222222/022222/ 0.2217138 222222/2022222/ 0.1285476 22222220/2222/2 -0.1127480 22222222/22220/ -0.0925871 22222220/22222/ 0.0868294 2222222/222220/ -0.0807734 2222222/02222/2 -0.0668671 222222/\/2222/2 0.0592853 2222222/22222/0 0.0581679 222222/222222/0 0.0554463 RESULTS FOR STATE 1.3 ===================== Coefficient of reference function: C(0) = 1.00000000 (fixed) 1.00000000 (relaxed) Energy contributions of configuration classes CLASS SQ.NORM ECORR1 ECORR2 +++++++++++++++++++++++++++++++++++++++++++++++++++ Internals 0.00067157 -0.00149889 0.79037733 Singles 0.03671047 -0.09058190 -0.19578606 Pairs 0.16018853 -0.64226511 -1.38820836 Total 1.19757058 -0.73434590 -0.79361708 +++++++++++++++++++++++++++++++++++++++++++++++++++ Reference energy -208.77560053 Nuclear energy 161.27557595 Kinetic energy 209.60494991 One electron energy -600.75611198 Two electron energy 229.91131841 Virial quotient -0.99982953 Correlation energy -0.79361708 !RSPT2 STATE 1.3 Energy -209.569217614874 Properties without orbital relaxation: !RSPT2 STATE 1.3 Dipole moment 0.00000000 0.00000000 0.35265842 Dipole moment /Debye 0.00000000 0.00000000 0.89630960 !RSPT expec <1.3|H|1.3> -209.458720175550 Correlation energy -0.81808398 !RSPT3 STATE 1.3 Energy -209.593684512487 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 2310.61 500 700 610 900 950 970 1001 129 960 1100 VAR GEOM BASINP SYMINP ZMAT AOBASIS BASIS P2S ABASIS S 1400 1410 1200 1210 1080 1600 1650 1300 1700 1380 T V H0 H01 AOSYM SMH MOLCAS ERIS OPER JKOP 2 9 20.24 500 610 700 1000 520 2100 2140 1001 2141 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF PROGRAMS * TOTAL RS3 RS3 RS3 RS3 MULTI INT RESTART CPU TIMES * 126.52 20.53 17.45 20.01 22.45 8.21 37.75 0.01 REAL TIME * 137.79 SEC DISK USED * 7.54 GB ********************************************************************************************************************************** RS3/aug-cc-pVTZ energy= -209.593684512487 RS3 RS3 RS3 RS3 MULTI -209.59368451 -209.75883153 -209.59593087 -209.75902562 -208.77560053 ********************************************************************************************************************************** Molpro calculation terminated