Working directory : /state/partition1/1191661/molpro.SMfihNOiY3/ Global scratch directory : /state/partition1/1191661/molpro.SMfihNOiY3/ Wavefunction directory : /home/boggio/wfu/ Main file repository : /state/partition1/1191661/molpro.SMfihNOiY3/ id : irsamc Nodes nprocs compute-13-1.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 ***,acetaldehyde, CASPT3(6,5)/aug-cc-pVTZ S0 and T1(n,pi*) calculation memory,2000,m file,2,acet_cas5_avtz_t1.wfu GEOMTYP=xyz BOHR GEOMETRY={ 7 CC3/aug-cc-pVTZ S0 optimised geometry C -0.00234503 0.00000000 0.87125063 C -1.75847785 0.00000000 -1.34973671 O 2.27947397 0.00000000 0.71968028 H -0.92904537 0.00000000 2.73929404 H -2.97955463 1.66046488 -1.25209463 H -2.97955463 -1.66046488 -1.25209463 H -0.70043433 0.00000000 -3.11066412} BASIS=AVTZ INT {MULTI occ,11,3 closed,8,1 wf,24,1,0 wf,24,2,2 canonical print,orbitals,civector} {RS3,shift=0.3 wf,24,1,0} {RS3,shift=0.3 wf,24,2,2} {RS3,shift=0.3,ipea=0.25 wf,24,1,0} {RS3,shift=0.3,ipea=0.25 wf,24,2,2} Commands initialized (810), CPU time= 0.01 sec, 661 directives. Default parameters read. Elapsed time= 0.10 sec Checking input... Passed 1 *** PROGRAM SYSTEM MOLPRO *** Copyright, TTI GmbH Stuttgart, 2015 Version 2021.2 linked Jun 2 2021 16:00:59 ********************************************************************************************************************************** LABEL * acetaldehyde, CASPT3(6,5)/aug-cc-pVTZ S0 and T1(n,pi*) calculation 64 bit serial version DATE: 06-Dec-21 TIME: 09:10:07 ********************************************************************************************************************************** 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 acet_cas5_avtz_t1.wfu assigned. Implementation=df Size= 22.28 MB PROGRAM * RESTART Reading variables from file 2 _FNUC = 0.00000000 _BASIS = AVTZ _ZUNIT = BOHR _NELEC = 24.00000000 _PROGRAM = RS2 _DMX = -0.47283391 _DMZ = -0.06319363 _DMX_SCF = -0.70592522 _DMY_SCF = 0.00000000 _DMZ_SCF = -0.04802332 _HOMO = 10.10000000 _EHOMO = -0.33708241 _LUMO = 3.20000000 _ELUMO = 0.29442782 _EMP2 = -153.39674071 _ENERGR = -152.87919204 _ENERGU = -153.36044074 _ENERGY = -153.39674071 _ENERGY_METHOD = RS2 _ENERGY_BASIS = aug-cc-pVTZ _ENERGY_AVRG = -152.95784346 _ENUC = 69.77934997 _IPROC_MPP = 0.00000000 _IPROC_MPPX = 0.00000000 _ORBITAL = 2142.20000000 _STATUS = 1.00000000 _DATE = 07-Oct-21 _LASTORB = MCSCF _PGROUP = Cs _TIME = 16:41:37 _DMX_CC(1:2) = 8.17960993 8.17960993 _DMY_CC(1:2) = -0.00000000 -0.00000000 _DMZ_CC(1:2) = 4.51027462 4.51027462 _DMX_NUC(1:2) = 0.08226552 0.08226552 _DMY_NUC(1:2) = 0.00000000 0.00000000 _DMZ_NUC(1:2) = 0.01096642 0.01096642 _SYM_CATION = 1.00000000 Geometry written to block 1 of record 700 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 2 11 22.28 500 610 700 1000 520 2100 2140 1001 2141 1002 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF BASIS 2142 MCSCF PROGRAMS * TOTAL RESTART CPU TIMES * 0.12 0.01 REAL TIME * 0.30 SEC DISK USED * 33.77 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 O S aug-cc-pVTZ selected for orbital group 2 Library entry O P aug-cc-pVTZ selected for orbital group 2 Library entry O D aug-cc-pVTZ selected for orbital group 2 Library entry O 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 Cs ATOMIC COORDINATES NR ATOM CHARGE X Y Z 1 C 6.00 -0.002345030 0.000000000 0.871250630 2 C 6.00 -1.758477850 0.000000000 -1.349736710 3 O 8.00 2.279473970 0.000000000 0.719680280 4 H 1.00 -0.929045370 0.000000000 2.739294040 5 H 1.00 -2.979554630 1.660464880 -1.252094630 6 H 1.00 -2.979554630 -1.660464880 -1.252094630 7 H 1.00 -0.700434330 0.000000000 -3.110664120 Bond lengths in Bohr (Angstrom) 1-2 2.831393163 1-3 2.286847507 1-4 2.085272093 2-5 2.063420969 2-6 2.063420969 ( 1.498308737) ( 1.210147585) ( 1.103478470) ( 1.091915353) ( 1.091915353) 2-7 2.054342093 ( 1.087111019) Bond angles 1-2-5 109.26393117 1-2-6 109.26393117 1-2-7 110.66728685 2-1-3 124.53308994 2-1-4 115.28148396 3-1-4 120.18542610 5-2-6 107.16539402 5-2-7 110.20264142 6-2-7 110.20264142 NUCLEAR CHARGE: 24 NUMBER OF PRIMITIVE AOS: 309 NUMBER OF SYMMETRY AOS: 274 NUMBER OF CONTRACTIONS: 230 ( 145A' + 85A" ) NUMBER OF INNER CORE ORBITALS: 0 ( 0A' + 0A" ) NUMBER OF OUTER CORE ORBITALS: 3 ( 3A' + 0A" ) NUMBER OF VALENCE ORBITALS: 16 ( 12A' + 4A" ) NUCLEAR REPULSION ENERGY 69.77934997 Eigenvalues of metric 1 0.297E-04 0.482E-04 0.633E-04 0.960E-04 0.128E-03 0.273E-03 0.362E-03 0.602E-03 2 0.931E-04 0.649E-03 0.983E-03 0.146E-02 0.322E-02 0.367E-02 0.407E-02 0.536E-02 Contracted 2-electron integrals neglected if value below 1.0D-12 AO integral compression algorithm 1 Integral accuracy 1.0D-12 1020.789 MB (compressed) written to integral file ( 60.9%) NUMBER OF SORTED TWO-ELECTRON INTEGRALS: 178772270. BUFFER LENGTH: 32768 NUMBER OF SEGMENTS: 12 SEGMENT LENGTH: 15999503 RECORD LENGTH: 524288 Memory used in sort: 16.56 MW SORT1 READ 209593537. AND WROTE 176902000. INTEGRALS IN 512 RECORDS. CPU TIME: 2.06 SEC, REAL TIME: 3.07 SEC SORT2 READ 176902000. AND WROTE 178772270. INTEGRALS IN 3894 RECORDS. CPU TIME: 1.92 SEC, REAL TIME: 2.54 SEC FILE SIZES: FILE 1: 1052.3 MBYTE, FILE 4: 2147.5 MBYTE, TOTAL: 3199.8 MBYTE OPERATOR DM FOR CENTER 0 COORDINATES: 0.000000 0.000000 0.000000 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 19 885.75 500 700 610 900 950 970 1002 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 11 22.28 500 610 700 1000 520 2100 2140 1001 2141 1002 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF BASIS 2142 MCSCF PROGRAMS * TOTAL INT RESTART CPU TIMES * 10.68 10.55 0.01 REAL TIME * 13.46 SEC DISK USED * 3.00 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: 9 ( 8 1 ) Number of active orbitals: 5 ( 3 2 ) Number of external orbitals: 216 ( 134 82 ) 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=2 Number of states: 1 Number of CSFs: 24 (26 determinants, 50 intermediate states) Molecular orbitals read from record 2142.2 Type=MCSCF/CANONICAL (state averaged) Wavefunction dump at record 2142.2 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: 1746 ( 26 closed/active, 1154 closed/virtual, 0 active/active, 566 active/virtual ) Total number of variables: 1824 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 5 4 0 -152.95784346 -152.95784346 -0.00000000 0.00000000 0.00000000 0.00000000 0.54E-09 2.21 CONVERGENCE REACHED! Final gradient: 0.00000000 ( 0.28E-10) Final energy: -152.95784346 Molecular orbital coefficients: Orbital Occupation Energy Cen Mu Typ Coefficients 1.1 2.00000 0.00000 3 1 s 0.99824 2.1 2.00000 0.00000 1 1 s 1.00022 3.1 2.00000 0.00000 2 1 s 1.00049 4.1 2.00000 0.00000 3 2 s 0.86931 3 1 px 0.28370 5.1 2.00000 0.00000 1 2 s 0.35047 2 2 s 0.71252 3 2 s -0.27143 5 1 s 0.40614 7 1 s 0.27364 6.1 2.00000 0.00000 1 2 s 0.55646 1 1 pz 0.25693 2 2 s -0.28239 2 1 pz 0.26323 4 1 s 0.58969 4 3 s -0.28973 5 1 s -0.25914 7 1 s -0.30085 7.1 2.00000 0.00000 1 1 pz -0.48408 2 1 px 0.56382 4 1 s -0.28856 5 1 s -0.52601 8.1 2.00000 0.00000 1 1 pz -0.33690 2 1 px -0.27552 2 1 pz 0.55453 4 1 s -0.33483 5 1 s 0.29876 7 1 s -0.69084 7 3 s 0.33686 9.1 1.00000 0.00000 1 2 s -0.36748 1 1 px -0.58218 3 1 px 0.76212 10.1 1.00000 0.00000 3 1 pz 0.91747 4 1 s -0.28550 11.1 1.00000 0.00000 1 2 s -0.92720 1 5 s -0.43519 1 1 px -1.15692 3 2 s 0.67812 3 4 s 0.51753 3 5 s 0.52866 3 1 px -1.24541 1.2 2.00000 0.00000 2 1 py 0.65895 5 1 s 0.83846 5 3 s -0.37952 2.2 1.00000 0.00000 1 1 py 0.44248 3 1 py 0.79336 3.2 1.00000 0.00000 1 1 py 0.86152 3 1 py -0.61996 CI Coefficients of symmetry 1 ============================= 220 20 0.95751396 220 02 -0.15555849 220 ba -0.14662346 220 ab 0.14662346 022 20 -0.06253484 b2a ab 0.05212724 a2b ba 0.05212724 Energy: -153.03649488 CI Coefficients of symmetry 2 ============================= 2a0 2a 0.98954795 2a0 a2 0.09972442 0a2 2a -0.06816361 Energy: -152.87919204 Results for state 1.1 ===================== !MCSCF STATE 1.1 Energy -153.036494879582 Nuclear energy 69.77934997 Kinetic energy 152.97161125 One electron energy -346.04545724 Two electron energy 123.22961239 Virial ratio 2.00042415 !MCSCF STATE 1.1 Dipole moment -1.01744172 0.00000000 -0.05631592 Dipole moment /Debye -2.58607890 0.00000000 -0.14314079 Results for state 1.2 ===================== !MCSCF STATE 1.2 Energy -152.879192041722 Nuclear energy 69.77934997 Kinetic energy 153.14335895 One electron energy -345.73353650 Two electron energy 123.07499449 Virial ratio 1.99827504 !MCSCF STATE 1.2 Dipole moment -0.45903777 0.00000000 -0.06987019 Dipole moment /Debye -1.16675764 0.00000000 -0.17759232 State-averaged charge density matrix saved on record 2142.2 (density set 1) Expectation values: (only non-zero values are shown) !MCSCF expec <1.1|DMX|1.1> -1.017441717723 au = -2.586078897704 Debye !MCSCF expec <1.2|DMX|1.2> -0.459037771033 au = -1.166757635586 Debye !MCSCF expec <1.1|DMZ|1.1> -0.056315918210 au = -0.143140786495 Debye !MCSCF expec <1.2|DMZ|1.2> -0.069870193854 au = -0.177592318810 Debye PSEUDO CANONICAL ORBITALS (STATE AVERAGED) ========================================== Orbital Occupation Energy Cen Mu Typ Coefficients 1.1 2.00000 -20.59959 3 1 s 0.99824 2.1 2.00000 -11.26820 1 1 s 1.00022 3.1 2.00000 -11.23467 2 1 s 1.00049 4.1 2.00000 -1.17974 3 2 s 0.86931 3 1 px 0.28370 5.1 2.00000 -1.00482 1 2 s 0.35047 2 2 s 0.71252 3 2 s -0.27143 5 1 s 0.40614 7 1 s 0.27364 6.1 2.00000 -0.77009 1 2 s 0.55646 1 1 pz 0.25693 2 2 s -0.28239 2 1 pz 0.26323 4 1 s 0.58969 4 3 s -0.28973 5 1 s -0.25914 7 1 s -0.30085 7.1 2.00000 -0.61827 1 1 pz -0.48408 2 1 px 0.56382 4 1 s -0.28856 5 1 s -0.52601 8.1 2.00000 -0.55415 1 1 pz -0.33690 2 1 px -0.27552 2 1 pz 0.55453 4 1 s -0.33483 5 1 s 0.29876 7 1 s -0.69084 7 3 s 0.33686 9.1 1.98231 -0.90327 1 2 s -0.36748 1 1 px -0.58218 3 1 px 0.76212 10.1 1.49951 -0.35724 3 1 pz 0.91747 4 1 s -0.28550 11.1 0.01816 1.02449 1 2 s -0.92720 1 5 s -0.43519 1 1 px -1.15692 3 2 s 0.67812 3 4 s 0.51753 3 5 s 0.52866 3 1 px -1.24541 1.2 2.00000 -0.57323 2 1 py 0.65895 5 1 s 0.83846 5 3 s -0.37952 2.2 1.94196 -0.55559 1 1 py 0.44248 3 1 py 0.79336 3.2 0.55807 0.06522 1 1 py 0.86152 3 1 py -0.61996 Canonical orbital dump (state averaged) at molpro section 2142.2 (Orbital set 2) Reoptimze the CI vectors with pseudo canonical orbitals CI Coefficients of symmetry 1 ============================= 220 20 0.95751396 220 02 -0.15555849 220 ba -0.14662346 220 ab 0.14662346 022 20 -0.06253484 b2a ab 0.05212724 a2b ba 0.05212724 Energy: -153.03649488 CI Coefficients of symmetry 2 ============================= 2a0 2a 0.98954795 2a0 a2 0.09972442 0a2 2a -0.06816361 Energy: -152.87919204 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 918.85 500 700 610 900 950 970 1002 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 11 22.28 500 610 700 1000 520 2100 2140 1001 2141 1002 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF BASIS 2142 MCSCF PROGRAMS * TOTAL MULTI INT RESTART CPU TIMES * 14.65 3.97 10.55 0.01 REAL TIME * 17.78 SEC DISK USED * 3.00 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: 24 Maximum number of shells: 5 Maximum number of spin couplings: 14 Reference space: 25 conf 28 CSFs N elec internal: 540 conf 755 CSFs N-1 el internal: 951 conf 2235 CSFs N-2 el internal: 876 conf 3263 CSFs Number of electrons in valence space: 18 Maximum number of open shell orbitals in reference space: 4 Maximum number of open shell orbitals in internal spaces: 8 Number of core orbitals: 3 ( 3 0 ) Number of closed-shell orbitals: 6 ( 5 1 ) Number of active orbitals: 5 ( 3 2 ) Number of external orbitals: 216 ( 134 82 ) Molecular orbitals read from record 2142.2 Type=MCSCF/CANONICAL (state averaged) Integral transformation finished. Total CPU: 1.45 sec, npass= 1 Memory used: 2.14 MW Number of p-space configurations: 2 Reference wavefunction optimized for reference space (refopt=1) State Reference Energy 1 -153.03649488 Number of blocks in overlap matrix: 4 Smallest eigenvalue: 0.23D-02 Number of N-2 electron functions: 121 Number of N-1 electron functions: 2235 Number of internal configurations: 392 Number of singly external configurations: 241510 Number of doubly external configurations: 1429432 Total number of contracted configurations: 1671334 Total number of uncontracted configurations: 38902486 Weight factors for SA-density in H0: 1.000000 FIMAX= 0.34D+00 FXMAX= 0.19D-01 DIAG= F F NOREF=1 NOINT=0 IHPPD=2 Nuclear energy: 69.77934997 Core energy: -154.13488741 Zeroth-order valence energy: -13.07281844 Zeroth-order total energy: -97.42835589 First-order energy: -55.60813899 Diagonal Coupling coefficients finished. Storage: 339452 words, CPU-Time: 0.00 seconds. Energy denominators for pairs finished in 0 passes. Storage: 246533 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 1.02450843 -0.00735253 -153.04384741 -0.00735253 -0.47002233 0.25D-01 0.89D-01 2.35 2 1 1 1.11394964 -0.50501387 -153.54150875 -0.49766134 0.00061125 0.38D-03 0.19D-03 2.59 3 1 1 1.11484764 -0.50712767 -153.54362255 -0.00211380 -0.00144585 0.16D-04 0.31D-05 2.83 4 1 1 1.11502346 -0.50724114 -153.54373602 -0.00011347 0.00004239 0.69D-06 0.23D-06 3.07 5 1 1 1.11506701 -0.50725704 -153.54375192 -0.00001590 -0.00005081 0.46D-07 0.85D-08 3.31 6 1 1 1.11507202 -0.50725875 -153.54375363 -0.00000171 0.00000179 0.29D-08 0.67D-09 3.56 7 1 1 1.11507427 -0.50725938 -153.54375426 -0.00000063 -0.00000247 0.23D-09 0.35D-10 3.80 8 1 1 1.11507447 -0.50725943 -153.54375431 -0.00000005 0.00000009 0.18D-10 0.29D-11 4.04 Energies without level shift correction: 8 1 1 1.11507447 -0.47273709 -153.50923197 Energy contributions for state 1.1: =================================== Energy contr. SQ.Norm of FOWF Space I -0.00310013 0.00127071 Space S -0.08070443 0.02419621 Space P -0.38893252 0.08960754 ===================================== Analysis of CPU times by interactions ===================================== I S P I 0.2% S 2.7% 2.0% P 0.5% 26.7% 8.7% Initialization: 56.9% Other: 2.2% Total CPU: 4.0 seconds ===================================== gnormi= 1.00127071 gnorms= 0.02419621 gnormp= 0.08960754 gnorm= 1.11507447 ecorri= -0.00310013 ecorrs= -0.08070443 ecorrp= -0.38893252 ecorr= -0.50725943 Reference coefficients greater than 0.0500000 ============================================= 22222220220 0.9575139 222222202/\ 0.2073569 22222220202 -0.1555585 22222/2\2/\ -0.0864800 22222022220 -0.0625348 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 0.00127071 -0.00310013 0.50060620 Singles 0.02419621 -0.08070433 -0.17319588 Pairs 0.08960754 -0.38893246 -0.83466975 Total 1.11507447 -0.47273692 -0.50725943 +++++++++++++++++++++++++++++++++++++++++++++++++++ Reference energy -153.03649488 Nuclear energy 69.77934997 Kinetic energy 153.25643965 One electron energy -345.72788975 Two electron energy 122.40478547 Virial quotient -1.00187473 Correlation energy -0.50725943 !RSPT2 STATE 1.1 Energy -153.543754310976 Properties without orbital relaxation: !RSPT2 STATE 1.1 Dipole moment -0.98860051 0.00000000 -0.07490143 Dipole moment /Debye -2.51277187 0.00000000 -0.19038046 !RSPT expec <1.1|H|1.1> -153.512657593222 Correlation energy -0.53095690 !RSPT3 STATE 1.1 Energy -153.567451778043 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 918.85 500 700 610 900 950 970 1002 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 11 22.28 500 610 700 1000 520 2100 2140 1001 2141 1002 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF BASIS 2142 MCSCF PROGRAMS * TOTAL RS3 MULTI INT RESTART CPU TIMES * 25.15 10.50 3.97 10.55 0.01 REAL TIME * 28.93 SEC DISK USED * 3.00 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: 2 Triplet Number of electrons: 24 Maximum number of shells: 4 Maximum number of spin couplings: 28 Reference space: 20 conf 24 CSFs N elec internal: 500 conf 930 CSFs N-1 el internal: 951 conf 3519 CSFs N-2 el internal: 752 conf 5580 CSFs Number of electrons in valence space: 18 Maximum number of open shell orbitals in reference space: 4 Maximum number of open shell orbitals in internal spaces: 8 Number of core orbitals: 3 ( 3 0 ) Number of closed-shell orbitals: 6 ( 5 1 ) Number of active orbitals: 5 ( 3 2 ) Number of external orbitals: 216 ( 134 82 ) Molecular orbitals read from record 2142.2 Type=MCSCF/CANONICAL (state averaged) Coulomb and exchange operators available. No transformation done. Number of p-space configurations: 3 Reference wavefunction optimized for reference space (refopt=1) State Reference Energy 1 -152.87919204 Number of blocks in overlap matrix: 4 Smallest eigenvalue: 0.47D-03 Number of N-2 electron functions: 121 Number of N-1 electron functions: 3519 Number of internal configurations: 479 Number of singly external configurations: 380962 Number of doubly external configurations: 1429432 Total number of contracted configurations: 1810873 Total number of uncontracted configurations: 66363453 Weight factors for SA-density in H0: 1.000000 FIMAX= 0.34D+00 FXMAX= 0.19D-01 DIAG= F F NOREF=1 NOINT=0 IHPPD=2 Nuclear energy: 69.77934997 Core energy: -154.13488741 Zeroth-order valence energy: -12.66484989 Zeroth-order total energy: -97.02038733 First-order energy: -55.85880471 Diagonal Coupling coefficients finished. Storage: 352478 words, CPU-Time: 0.01 seconds. Energy denominators for pairs finished in 0 passes. Storage: 252900 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 1.03323007 -0.00996902 -152.88916106 -0.00996902 -0.48223030 0.33D-01 0.91D-01 0.13 2 1 1 1.12727251 -0.52562897 -153.40482101 -0.51565995 0.00002658 0.55D-03 0.17D-03 0.47 3 1 1 1.12845661 -0.52815669 -153.40734873 -0.00252771 -0.00156924 0.20D-04 0.37D-05 0.82 4 1 1 1.12870364 -0.52830072 -153.40749276 -0.00014403 0.00001392 0.94D-06 0.25D-06 1.17 5 1 1 1.12876483 -0.52832236 -153.40751440 -0.00002164 -0.00005590 0.55D-07 0.11D-07 1.52 6 1 1 1.12877262 -0.52832494 -153.40751698 -0.00000258 0.00000034 0.38D-08 0.87D-09 1.88 7 1 1 1.12877575 -0.52832582 -153.40751786 -0.00000088 -0.00000275 0.26D-09 0.46D-10 2.23 8 1 1 1.12877613 -0.52832591 -153.40751795 -0.00000009 -0.00000000 0.21D-10 0.44D-11 2.58 Energies without level shift correction: 8 1 1 1.12877613 -0.48969307 -153.36888511 Energy contributions for state 1.2: =================================== Energy contr. SQ.Norm of FOWF Space I -0.00655889 0.00353966 Space S -0.09710410 0.03410480 Space P -0.38603008 0.09113168 ===================================== Analysis of CPU times by interactions ===================================== I S P I 0.4% S 6.2% 6.6% P 0.8% 65.1% 12.8% Initialization: 3.1% Other: 5.0% Total CPU: 2.6 seconds ===================================== gnormi= 1.00353966 gnorms= 0.03410480 gnormp= 0.09113168 gnorm= 1.12877613 ecorri= -0.00655889 ecorrs= -0.09710410 ecorrp= -0.38603008 ecorr= -0.52832591 Reference coefficients greater than 0.0500000 ============================================= 222222/022/ 0.9895480 222222/02/2 0.0997244 222220/222/ -0.0681636 22222//\2/2 -0.0548124 RESULTS FOR STATE 1.2 ===================== Coefficient of reference function: C(0) = 1.00000000 (fixed) 1.00000000 (relaxed) Energy contributions of configuration classes CLASS SQ.NORM ECORR1 ECORR2 +++++++++++++++++++++++++++++++++++++++++++++++++++ Internals 0.00353966 -0.00655888 0.51417303 Singles 0.03410480 -0.09710397 -0.20952951 Pairs 0.09113168 -0.38603002 -0.83296943 Total 1.12877613 -0.48969286 -0.52832591 +++++++++++++++++++++++++++++++++++++++++++++++++++ Reference energy -152.87919204 Nuclear energy 69.77934997 Kinetic energy 153.49460318 One electron energy -345.44777576 Two electron energy 122.26090784 Virial quotient -0.99943265 Correlation energy -0.52832591 !RSPT2 STATE 1.2 Energy -153.407517953562 Properties without orbital relaxation: !RSPT2 STATE 1.2 Dipole moment -0.47617073 0.00000000 -0.06340266 Dipole moment /Debye -1.21030528 0.00000000 -0.16115350 !RSPT expec <1.2|H|1.2> -153.357680212366 Correlation energy -0.54010604 !RSPT3 STATE 1.2 Energy -153.419298085336 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 918.85 500 700 610 900 950 970 1002 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 11 22.28 500 610 700 1000 520 2100 2140 1001 2141 1002 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF BASIS 2142 MCSCF PROGRAMS * TOTAL RS3 RS3 MULTI INT RESTART CPU TIMES * 34.94 9.79 10.50 3.97 10.55 0.01 REAL TIME * 39.23 SEC DISK USED * 3.00 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: 24 Maximum number of shells: 5 Maximum number of spin couplings: 14 Reference space: 25 conf 28 CSFs N elec internal: 540 conf 755 CSFs N-1 el internal: 951 conf 2235 CSFs N-2 el internal: 876 conf 3263 CSFs Number of electrons in valence space: 18 Maximum number of open shell orbitals in reference space: 4 Maximum number of open shell orbitals in internal spaces: 8 Number of core orbitals: 3 ( 3 0 ) Number of closed-shell orbitals: 6 ( 5 1 ) Number of active orbitals: 5 ( 3 2 ) Number of external orbitals: 216 ( 134 82 ) Molecular orbitals read from record 2142.2 Type=MCSCF/CANONICAL (state averaged) Coulomb and exchange operators available. No transformation done. Number of p-space configurations: 2 Reference wavefunction optimized for reference space (refopt=1) State Reference Energy 1 -153.03649488 Number of blocks in overlap matrix: 4 Smallest eigenvalue: 0.23D-02 Number of N-2 electron functions: 121 Number of N-1 electron functions: 2235 Number of internal configurations: 392 Number of singly external configurations: 241510 Number of doubly external configurations: 1429432 Total number of contracted configurations: 1671334 Total number of uncontracted configurations: 38902486 Weight factors for SA-density in H0: 1.000000 FIMAX= 0.34D+00 FXMAX= 0.19D-01 DIAG= F F NOREF=1 NOINT=0 IHPPD=2 Nuclear energy: 69.77934997 Core energy: -154.13488741 Zeroth-order valence energy: -8.63119009 Zeroth-order total energy: -92.98672753 First-order energy: -60.04976735 Diagonal Coupling coefficients finished. Storage: 339452 words, CPU-Time: 0.00 seconds. Energy denominators for pairs finished in 0 passes. Storage: 246533 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 1.02308079 -0.00692424 -153.04341912 -0.00692424 -0.46811560 0.23D-01 0.89D-01 0.13 2 1 1 1.11255257 -0.50293653 -153.53943141 -0.49601230 0.00038310 0.32D-03 0.18D-03 0.38 3 1 1 1.11340804 -0.50496340 -153.54145828 -0.00202687 -0.00137543 0.14D-04 0.29D-05 0.62 4 1 1 1.11358953 -0.50507474 -153.54156962 -0.00011134 0.00002797 0.52D-06 0.21D-06 0.87 5 1 1 1.11363057 -0.50508964 -153.54158452 -0.00001490 -0.00004690 0.33D-07 0.78D-08 1.12 6 1 1 1.11363599 -0.50509145 -153.54158633 -0.00000181 0.00000087 0.19D-08 0.59D-09 1.37 7 1 1 1.11363804 -0.50509203 -153.54158691 -0.00000058 -0.00000220 0.13D-09 0.31D-10 1.62 8 1 1 1.11363827 -0.50509208 -153.54158696 -0.00000006 0.00000003 0.90D-11 0.25D-11 1.87 Energies without level shift correction: 8 1 1 1.11363827 -0.47100060 -153.50749548 Energy contributions for state 1.1: =================================== Energy contr. SQ.Norm of FOWF Space I -0.00303562 0.00121233 Space S -0.07954124 0.02311307 Space P -0.38842374 0.08931288 ===================================== Analysis of CPU times by interactions ===================================== I S P I 0.5% S 7.5% 3.7% P 1.6% 57.8% 19.8% Initialization: 4.3% Other: 4.8% Total CPU: 1.9 seconds ===================================== gnormi= 1.00121233 gnorms= 0.02311307 gnormp= 0.08931288 gnorm= 1.11363827 ecorri= -0.00303562 ecorrs= -0.07954124 ecorrp= -0.38842374 ecorr= -0.50509208 Reference coefficients greater than 0.0500000 ============================================= 22222220220 0.9575139 222222202/\ 0.2073569 22222220202 -0.1555585 22222/2\2/\ -0.0864800 22222022220 -0.0625348 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 0.00121233 -0.00303561 0.49858124 Singles 0.02311307 -0.07954115 -0.17059693 Pairs 0.08931288 -0.38842368 -0.83307640 Total 1.11363827 -0.47100045 -0.50509208 +++++++++++++++++++++++++++++++++++++++++++++++++++ Reference energy -153.03649488 Nuclear energy 69.77934997 Kinetic energy 153.26473298 One electron energy -345.73636202 Two electron energy 122.41542509 Virial quotient -1.00180638 Correlation energy -0.50509208 !RSPT2 STATE 1.1 Energy -153.541586963641 Properties without orbital relaxation: !RSPT2 STATE 1.1 Dipole moment -0.99440330 0.00000000 -0.07025022 Dipole moment /Debye -2.52752108 0.00000000 -0.17855824 !RSPT expec <1.1|H|1.1> -153.512732709344 Correlation energy -0.53035669 !RSPT3 STATE 1.1 Energy -153.566851570322 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 918.85 500 700 610 900 950 970 1002 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 11 22.28 500 610 700 1000 520 2100 2140 1001 2141 1002 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF BASIS 2142 MCSCF PROGRAMS * TOTAL RS3 RS3 RS3 MULTI INT RESTART CPU TIMES * 43.31 8.37 9.79 10.50 3.97 10.55 0.01 REAL TIME * 48.05 SEC DISK USED * 3.00 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: 2 Triplet Number of electrons: 24 Maximum number of shells: 4 Maximum number of spin couplings: 28 Reference space: 20 conf 24 CSFs N elec internal: 500 conf 930 CSFs N-1 el internal: 951 conf 3519 CSFs N-2 el internal: 752 conf 5580 CSFs Number of electrons in valence space: 18 Maximum number of open shell orbitals in reference space: 4 Maximum number of open shell orbitals in internal spaces: 8 Number of core orbitals: 3 ( 3 0 ) Number of closed-shell orbitals: 6 ( 5 1 ) Number of active orbitals: 5 ( 3 2 ) Number of external orbitals: 216 ( 134 82 ) Molecular orbitals read from record 2142.2 Type=MCSCF/CANONICAL (state averaged) Coulomb and exchange operators available. No transformation done. Number of p-space configurations: 3 Reference wavefunction optimized for reference space (refopt=1) State Reference Energy 1 -152.87919204 Number of blocks in overlap matrix: 4 Smallest eigenvalue: 0.47D-03 Number of N-2 electron functions: 121 Number of N-1 electron functions: 3519 Number of internal configurations: 479 Number of singly external configurations: 380962 Number of doubly external configurations: 1429432 Total number of contracted configurations: 1810873 Total number of uncontracted configurations: 66363453 Weight factors for SA-density in H0: 1.000000 FIMAX= 0.34D+00 FXMAX= 0.19D-01 DIAG= F F NOREF=1 NOINT=0 IHPPD=2 Nuclear energy: 69.77934997 Core energy: -154.13488741 Zeroth-order valence energy: -8.42629921 Zeroth-order total energy: -92.78183665 First-order energy: -60.09735539 Diagonal Coupling coefficients finished. Storage: 352478 words, CPU-Time: 0.01 seconds. Energy denominators for pairs finished in 0 passes. Storage: 252900 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 1.02811022 -0.00843307 -152.88762511 -0.00843307 -0.47441588 0.28D-01 0.89D-01 0.12 2 1 1 1.11984448 -0.51521372 -153.39440576 -0.50678065 -0.00009190 0.39D-03 0.15D-03 0.47 3 1 1 1.12072411 -0.51740474 -153.39659679 -0.00219103 -0.00137994 0.14D-04 0.31D-05 0.82 4 1 1 1.12094486 -0.51752947 -153.39672152 -0.00012473 0.00000594 0.53D-06 0.20D-06 1.17 5 1 1 1.12099087 -0.51754584 -153.39673788 -0.00001636 -0.00004589 0.31D-07 0.77D-08 1.52 6 1 1 1.12099745 -0.51754799 -153.39674004 -0.00000216 -0.00000007 0.17D-08 0.55D-09 1.87 7 1 1 1.12099961 -0.51754860 -153.39674064 -0.00000060 -0.00000209 0.12D-09 0.28D-10 2.22 8 1 1 1.12099990 -0.51754866 -153.39674071 -0.00000007 -0.00000002 0.76D-11 0.22D-11 2.57 Energies without level shift correction: 8 1 1 1.12099990 -0.48124869 -153.36044074 Energy contributions for state 1.2: =================================== Energy contr. SQ.Norm of FOWF Space I -0.00595012 0.00278367 Space S -0.09205189 0.02886705 Space P -0.38324668 0.08934918 ===================================== Analysis of CPU times by interactions ===================================== I S P I 0.4% S 5.4% 5.4% P 0.8% 65.8% 14.4% Initialization: 2.7% Other: 5.1% Total CPU: 2.6 seconds ===================================== gnormi= 1.00278367 gnorms= 0.02886705 gnormp= 0.08934918 gnorm= 1.12099990 ecorri= -0.00595012 ecorrs= -0.09205189 ecorrp= -0.38324668 ecorr= -0.51754866 Reference coefficients greater than 0.0500000 ============================================= 222222/022/ 0.9895480 222222/02/2 0.0997244 222220/222/ -0.0681636 22222//\2/2 -0.0548124 RESULTS FOR STATE 1.2 ===================== Coefficient of reference function: C(0) = 1.00000000 (fixed) 1.00000000 (relaxed) Energy contributions of configuration classes CLASS SQ.NORM ECORR1 ECORR2 +++++++++++++++++++++++++++++++++++++++++++++++++++ Internals 0.00278367 -0.00595011 0.50475064 Singles 0.02886705 -0.09205180 -0.19799040 Pairs 0.08934918 -0.38324663 -0.82430891 Total 1.12099990 -0.48124854 -0.51754866 +++++++++++++++++++++++++++++++++++++++++++++++++++ Reference energy -152.87919204 Nuclear energy 69.77934997 Kinetic energy 153.48828807 One electron energy -345.45820164 Two electron energy 122.28211097 Virial quotient -0.99940355 Correlation energy -0.51754866 !RSPT2 STATE 1.2 Energy -153.396740705376 Properties without orbital relaxation: !RSPT2 STATE 1.2 Dipole moment -0.47283391 0.00000000 -0.06319363 Dipole moment /Debye -1.20182391 0.00000000 -0.16062220 !RSPT expec <1.2|H|1.2> -153.359421725546 Correlation energy -0.53833744 !RSPT3 STATE 1.2 Energy -153.417529484024 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 918.85 500 700 610 900 950 970 1002 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 11 22.28 500 610 700 1000 520 2100 2140 1001 2141 1002 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF BASIS 2142 MCSCF PROGRAMS * TOTAL RS3 RS3 RS3 RS3 MULTI INT RESTART CPU TIMES * 53.13 9.82 8.37 9.79 10.50 3.97 10.55 0.01 REAL TIME * 58.35 SEC DISK USED * 3.00 GB ********************************************************************************************************************************** RS3/aug-cc-pVTZ energy= -153.417529484024 RS3 RS3 RS3 RS3 MULTI -153.41752948 -153.56685157 -153.41929809 -153.56745178 -152.87919204 ********************************************************************************************************************************** Molpro calculation terminated