Working directory : /state/partition1/1198766/molpro.bl2JHMRxFE/ Global scratch directory : /state/partition1/1198766/molpro.bl2JHMRxFE/ Wavefunction directory : /home/boggio/wfu/ Main file repository : /state/partition1/1198766/molpro.bl2JHMRxFE/ id : irsamc Nodes nprocs compute-1-4.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= 0.01 sec ***,thiopropynal, CASPT3(8,7)/aug-cc-pVTZ 1Ap,1As calculation memory,2000,m file,2,thioprop_sa2cas7_avtz_as.wfu GEOMTYP=xyz BOHR GEOMETRY={ 6 CC3/aug-cc-pVTZ S0 optimised geometry C -0.00382924 0.00000000 -1.25249909 C -2.27832423 0.00000000 0.15152736 C -4.26309583 0.00000000 1.29548793 S 2.81920288 0.00000000 -0.00828974 H -0.23056990 0.00000000 -3.28862183 H -5.97712967 0.00000000 2.33206931} BASIS=AVTZ INT {MULTI occ,16,5 closed,13,1 wf,36,1,0 wf,36,2,0 canonical print,orbitals,civector} {RS3,shift=0.3 wf,36,1,0} {RS3,shift=0.3 wf,36,2,0} {RS3,shift=0.3,ipea=0.25 wf,36,1,0} {RS3,shift=0.3,ipea=0.25 wf,36,2,0} Commands initialized (810), CPU time= 0.01 sec, 661 directives. Default parameters read. Elapsed time= 0.13 sec Checking input... Passed 1 *** PROGRAM SYSTEM MOLPRO *** Copyright, TTI GmbH Stuttgart, 2015 Version 2021.2 linked Jun 2 2021 16:00:59 ********************************************************************************************************************************** LABEL * thiopropynal, CASPT3(8,7)/aug-cc-pVTZ 1Ap,1As calculation 64 bit serial version DATE: 09-Feb-22 TIME: 15:09:36 ********************************************************************************************************************************** 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 thioprop_sa2cas7_avtz_as.wfu assigned. Implementation=df Size= 20.07 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(1:2) = -0.74093469 -0.23101401 _DMY(2) = 0.00000000 _DMZ(1:2) = -0.19715717 -0.17669203 _DMX_SCF = -0.96095538 _DMY_SCF = 0.00000000 _DMZ_SCF = -0.20345835 _HOMO = 15.10000000 _EHOMO = -0.35521203 _LUMO = 4.20000000 _ELUMO = 0.02172026 _ENERGY(1:2) = -512.34872191 -512.27286909 _ENERGY_METHOD = MULTI _ENERGY_BASIS = aug-cc-pVTZ _ENUC = 115.82702136 _IPROC_MPP = 0.00000000 _IPROC_MPPX = 0.00000000 _ORBITAL = 2141.20000000 _STATUS = 1.00000000 _VERSION = 0.20190010D+07 _DATE = 07-Oct-19 _LASTORB = MCSCF _MACHINE = 64 bit serial version _OUTPUT = /home/boggio/THIOPROPYNAL/molpro.xml _PGROUP = Cs _TIME = 12:38:11 _LIBMOL = /home/thierry/PROGRAMS/Molpro2018/Molpro_release/lib/ _DMX_CC(1:2) = -4.92843117 -4.92843117 _DMY_CC(1:2) = -0.00000000 -0.00000000 _DMZ_CC(1:2) = 1.16947712 1.16947712 _DMX_NUC(1:2) = -0.37194929 -0.37194929 _DMY_NUC(1:2) = 0.00000000 0.00000000 _DMZ_NUC(1:2) = 0.07790884 0.07790884 _TRDMX = -0.00000000 _TRDMY = 0.00573932 _TRDMZ = -0.00000000 Geometry written to block 1 of record 700 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 2 9 20.07 500 610 700 1000 520 2100 2140 1001 2141 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF PROGRAMS * TOTAL RESTART CPU TIMES * 0.19 0.02 REAL TIME * 0.60 SEC DISK USED * 31.55 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 S S aug-cc-pVTZ selected for orbital group 2 Library entry S P aug-cc-pVTZ selected for orbital group 2 Library entry S D aug-cc-pVTZ selected for orbital group 2 Library entry S 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 -0.003829240 0.000000000 -1.252499090 2 C 6.00 -2.278324230 0.000000000 0.151527360 3 C 6.00 -4.263095830 0.000000000 1.295487930 4 S 16.00 2.819202880 0.000000000 -0.008289740 5 H 1.00 -0.230569900 0.000000000 -3.288621830 6 H 1.00 -5.977129670 0.000000000 2.332069310 Bond lengths in Bohr (Angstrom) 1-2 2.672941775 1-4 3.085055471 1-5 2.048708652 2-3 2.290843532 3-6 2.003100837 ( 1.414459873) ( 1.632541050) ( 1.084129930) ( 1.212262191) ( 1.059995314) Bond angles 1-2-3 178.27112831 2-1-4 124.52854697 2-1-5 115.33245834 2-3-6 178.79388329 4-1-5 120.13899470 NUCLEAR CHARGE: 36 NUMBER OF PRIMITIVE AOS: 339 NUMBER OF SYMMETRY AOS: 299 NUMBER OF CONTRACTIONS: 234 ( 155A' + 79A" ) NUMBER OF INNER CORE ORBITALS: 1 ( 1A' + 0A" ) NUMBER OF OUTER CORE ORBITALS: 7 ( 6A' + 1A" ) NUMBER OF VALENCE ORBITALS: 18 ( 14A' + 4A" ) NUCLEAR REPULSION ENERGY 115.82702136 Eigenvalues of metric 1 0.759E-05 0.109E-04 0.247E-04 0.284E-04 0.878E-04 0.104E-03 0.113E-03 0.195E-03 2 0.377E-03 0.755E-03 0.193E-02 0.273E-02 0.426E-02 0.467E-02 0.524E-02 0.597E-02 Contracted 2-electron integrals neglected if value below 1.0D-12 AO integral compression algorithm 1 Integral accuracy 1.0D-12 1016.070 MB (compressed) written to integral file ( 57.3%) NUMBER OF SORTED TWO-ELECTRON INTEGRALS: 192697675. BUFFER LENGTH: 32768 NUMBER OF SEGMENTS: 13 SEGMENT LENGTH: 15999503 RECORD LENGTH: 524288 Memory used in sort: 16.56 MW SORT1 READ 221498490. AND WROTE 187482418. INTEGRALS IN 541 RECORDS. CPU TIME: 3.08 SEC, REAL TIME: 4.84 SEC SORT2 READ 187482418. AND WROTE 192697675. INTEGRALS IN 3876 RECORDS. CPU TIME: 5.31 SEC, REAL TIME: 6.41 SEC FILE SIZES: FILE 1: 1047.6 MBYTE, FILE 4: 2269.2 MBYTE, TOTAL: 3316.8 MBYTE OPERATOR DM FOR CENTER 0 COORDINATES: 0.000000 0.000000 0.000000 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 19 897.19 500 700 610 900 950 970 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 20.07 500 610 700 1000 520 2100 2140 1001 2141 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF PROGRAMS * TOTAL INT RESTART CPU TIMES * 27.37 27.17 0.02 REAL TIME * 33.78 SEC DISK USED * 3.11 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: 14 ( 13 1 ) Number of active orbitals: 7 ( 3 4 ) Number of external orbitals: 213 ( 139 74 ) State symmetry 1 Number of active electrons: 8 Spin symmetry=Singlet Space symmetry=1 Number of states: 1 Number of CSFs: 254 (617 determinants, 1225 intermediate states) State symmetry 2 Number of active electrons: 8 Spin symmetry=Singlet Space symmetry=2 Number of states: 1 Number of CSFs: 236 (608 determinants, 1225 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: 2637 ( 43 closed/active, 1881 closed/virtual, 0 active/active, 713 active/virtual ) Total number of variables: 3862 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 14 35 0 -512.31079550 -512.31079550 -0.00000000 0.00001877 0.00000000 0.00000000 0.39E-08 6.01 CONVERGENCE REACHED! Final gradient: 0.00000000 ( 0.17E-08) Final energy: -512.31079550 Molecular orbital coefficients: Orbital Occupation Energy Cen Mu Typ Coefficients 1.1 2.00000 0.00000 4 1 s 1.00003 2.1 2.00000 0.00000 1 1 s 1.00013 3.1 2.00000 0.00000 2 1 s 0.97391 4.1 2.00000 0.00000 3 1 s 0.97440 5.1 2.00000 0.00000 4 2 s 0.99841 6.1 2.00000 0.00000 4 1 px 0.90531 4 1 pz 0.41720 7.1 2.00000 0.00000 4 1 px -0.41761 4 1 pz 0.90586 8.1 2.00000 0.00000 1 2 s 0.61154 2 2 s 0.47201 2 4 s -0.28318 3 2 s 0.25423 4 3 s 0.44898 9.1 2.00000 0.00000 2 2 s 0.51242 2 4 s -0.31571 2 1 px -0.26270 3 2 s 0.61063 4 3 s -0.41224 10.1 2.00000 0.00000 1 2 s -0.38269 1 1 px 0.35295 2 1 px -0.32908 3 2 s 0.36362 4 3 s 0.60875 5 1 s -0.26766 11.1 2.00000 0.00000 2 2 s 0.34200 3 2 s -0.30208 3 4 s -0.36517 3 1 px 0.47413 3 1 pz -0.28998 5 1 s -0.33813 6 1 s -0.66805 6 3 s 0.34866 12.1 2.00000 0.00000 1 1 pz 0.54783 2 1 px 0.42972 3 1 px -0.33934 5 1 s -0.56426 6 1 s 0.32030 13.1 2.00000 0.00000 1 1 px -0.45904 1 1 pz -0.28980 4 3 s 0.35961 4 2 px 0.62578 4 2 pz 0.25273 5 1 s 0.27408 14.1 1.00000 0.00000 2 1 px 0.31257 2 1 pz 0.54752 3 1 px 0.32048 3 1 pz 0.54506 15.1 1.00000 0.00000 4 2 px -0.37722 4 2 pz 0.88265 16.1 1.00000 0.00000 2 1 px -0.48626 2 1 pz -0.82048 3 1 px 0.48066 3 1 pz 0.81448 1.2 2.00000 0.00000 4 1 py 0.99870 2.2 1.00000 0.00000 1 1 py 0.30883 2 1 py 0.59596 3 1 py 0.52139 3.2 1.00000 0.00000 1 1 py 0.35552 3 1 py -0.29811 4 2 py 0.76493 4.2 1.00000 0.00000 1 1 py 0.74990 3 1 py -0.35676 4 2 py -0.59301 5.2 1.00000 0.00000 1 1 py -0.40300 2 1 py 0.97631 3 1 py -0.87862 CI Coefficients of symmetry 1 ============================= 220 2200 0.91218743 220 2020 -0.20259142 220 2ba0 -0.16606968 220 2ab0 0.16606968 022 2200 -0.12453660 220 0202 -0.08222576 a2b b20a -0.06194866 b2a a20b -0.06194866 220 baab 0.05411766 220 abba 0.05411766 Energy: -512.34872191 CI Coefficients of symmetry 2 ============================= 2b0 22a0 0.65971681 2a0 22b0 -0.65971681 2b0 2a20 0.17021530 2a0 2b20 -0.17021530 0b2 22a0 -0.09053975 0a2 22b0 0.09053975 2b0 a2ba 0.06365808 2a0 b2ab 0.06365808 2b0 02a2 -0.06262753 2a0 02b2 0.06262753 Energy: -512.27286909 Results for state 1.1 ===================== !MCSCF STATE 1.1 Energy -512.348721914489 Nuclear energy 115.82702136 Kinetic energy 512.28106659 One electron energy -933.69460126 Two electron energy 305.51885798 Virial ratio 2.00013207 !MCSCF STATE 1.1 Dipole moment -0.74093472 0.00000000 -0.19715716 Dipole moment /Debye -1.88314486 0.00000000 -0.50109069 Results for state 1.2 ===================== !MCSCF STATE 1.2 Energy -512.272869085474 Nuclear energy 115.82702136 Kinetic energy 512.34626071 One electron energy -933.31779232 Two electron energy 305.21790187 Virial ratio 1.99985675 !MCSCF STATE 1.2 Dipole moment -0.23101403 0.00000000 -0.17669202 Dipole moment /Debye -0.58714063 0.00000000 -0.44907690 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|DMX|1.1> -0.740934718297 au = -1.883144861328 Debye !MCSCF expec <1.2|DMX|1.2> -0.231014028365 au = -0.587140634213 Debye !MCSCF expec <1.1|DMZ|1.1> -0.197157158397 au = -0.501090690638 Debye !MCSCF expec <1.2|DMZ|1.2> -0.176692019588 au = -0.449076903146 Debye Transition values: (only non-zero values with the ground state are shown) !MCSCF trans <1.1|DMY|1.2> 0.005739323075 au = 0.014586948742 Debye PSEUDO CANONICAL ORBITALS (STATE AVERAGED) ========================================== Orbital Occupation Energy Cen Mu Typ Coefficients 1.1 2.00000 -91.97982 4 1 s 1.00003 2.1 2.00000 -11.29781 1 1 s 1.00013 3.1 2.00000 -11.23567 2 1 s 0.97391 4.1 2.00000 -11.22765 3 1 s 0.97440 5.1 2.00000 -8.98209 4 2 s 0.99841 6.1 2.00000 -6.66226 4 1 px 0.90531 4 1 pz 0.41720 7.1 2.00000 -6.66109 4 1 px -0.41761 4 1 pz 0.90586 8.1 2.00000 -1.10402 1 2 s 0.61154 2 2 s 0.47201 2 4 s -0.28318 3 2 s 0.25423 4 3 s 0.44898 9.1 2.00000 -1.01254 2 2 s 0.51242 2 4 s -0.31571 2 1 px -0.26270 3 2 s 0.61063 4 3 s -0.41224 10.1 2.00000 -0.85369 1 2 s -0.38269 1 1 px 0.35295 2 1 px -0.32908 3 2 s 0.36362 4 3 s 0.60875 5 1 s -0.26766 11.1 2.00000 -0.72384 2 2 s 0.34200 3 2 s -0.30208 3 4 s -0.36517 3 1 px 0.47413 3 1 pz -0.28998 5 1 s -0.33813 6 1 s -0.66805 6 3 s 0.34866 12.1 2.00000 -0.65969 1 1 pz 0.54783 2 1 px 0.42972 3 1 px -0.33934 5 1 s -0.56426 6 1 s 0.32030 13.1 2.00000 -0.55718 1 1 px -0.45904 1 1 pz -0.28980 4 3 s 0.35961 4 2 px 0.62578 4 2 pz 0.25273 5 1 s 0.27408 14.1 1.93729 -0.40492 2 1 px 0.30593 2 1 pz 0.54788 3 1 px 0.32019 3 1 pz 0.54163 15.1 1.50048 -0.29244 4 2 px -0.37914 4 2 pz 0.87946 16.1 0.06179 0.29816 2 1 px -0.48678 2 1 pz -0.82069 3 1 px 0.48049 3 1 pz 0.81401 1.2 2.00000 -6.66097 4 1 py 0.99870 2.2 1.93010 -0.47347 1 1 py 0.44472 2 1 py 0.46039 3 1 py 0.34048 4 2 py 0.47086 3.2 1.88976 -0.36945 2 1 py -0.43448 3 1 py -0.48018 4 2 py 0.63345 4.2 0.62143 -0.05170 1 1 py 0.72237 3 1 py -0.41913 4 2 py -0.58396 5.2 0.05916 0.34977 1 1 py -0.44131 2 1 py 0.97402 3 1 py -0.85895 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 2200 0.90931038 220 2ba0 -0.16118856 220 2ab0 0.16118856 220 2020 -0.14019371 022 2200 -0.12291864 220 0220 -0.10544193 220 ab20 0.08514116 220 ba20 -0.08514116 220 b2a0 -0.06788784 220 a2b0 0.06788784 220 2002 -0.05848490 a2b 2b0a 0.05745449 b2a 2a0b 0.05745449 220 baab 0.05720250 220 abba 0.05720250 Energy: -512.34872191 CI Coefficients of symmetry 2 ============================= 2b0 22a0 0.65798061 2a0 22b0 -0.65798061 2b0 2a20 0.13075300 2a0 2b20 -0.13075300 2a0 b220 -0.10651736 2b0 a220 0.10651736 0b2 22a0 -0.09017450 0a2 22b0 0.09017450 2b0 a2ba 0.05979339 2a0 b2ab 0.05979339 Energy: -512.27286909 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 972.54 500 700 610 900 950 970 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 20.08 500 610 700 1000 520 2100 2140 1001 2141 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF PROGRAMS * TOTAL MULTI INT RESTART CPU TIMES * 37.97 10.60 27.17 0.02 REAL TIME * 45.15 SEC DISK USED * 3.11 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: 6 Maximum number of spin couplings: 42 Reference space: 185 conf 254 CSFs N elec internal: 5334 conf 10696 CSFs N-1 el internal: 8121 conf 28252 CSFs N-2 el internal: 6600 conf 37750 CSFs Number of electrons in valence space: 20 Maximum number of open shell orbitals in reference space: 6 Maximum number of open shell orbitals in internal spaces: 10 Number of core orbitals: 8 ( 7 1 ) Number of closed-shell orbitals: 6 ( 6 0 ) Number of active orbitals: 7 ( 3 4 ) Number of external orbitals: 213 ( 139 74 ) Molecular orbitals read from record 2141.2 Type=MCSCF/CANONICAL (state averaged) Integral transformation finished. Total CPU: 3.07 sec, npass= 1 Memory used: 2.93 MW Number of p-space configurations: 12 Reference wavefunction optimized for reference space (refopt=1) State Reference Energy 1 -512.34872191 Number of blocks in overlap matrix: 4 Smallest eigenvalue: 0.19D-02 Number of N-2 electron functions: 169 Number of N-1 electron functions: 28252 Number of internal configurations: 5420 Number of singly external configurations: 3002988 Number of doubly external configurations: 1944631 Total number of contracted configurations: 4953039 Total number of uncontracted configurations: 456820436 Weight factors for SA-density in H0: 1.000000 FIMAX= 0.42D-01 FXMAX= 0.10D-01 DIAG= F F NOREF=1 NOINT=0 IHPPD=2 Nuclear energy: 115.82702136 Core energy: -559.20890571 Zeroth-order valence energy: -12.93068257 Zeroth-order total energy: -456.31256692 First-order energy: -56.03615499 Diagonal Coupling coefficients finished. Storage: 2172341 words, CPU-Time: 0.11 seconds. Energy denominators for pairs finished in 0 passes. Storage: 344452 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 1.04474712 -0.01342414 -512.36214605 -0.01342414 -0.48996606 0.45D-01 0.11D+00 5.52 2 1 1 1.15446998 -0.53956335 -512.88828526 -0.52613921 -0.00029596 0.18D-03 0.16D-03 9.81 3 1 1 1.15460321 -0.54045385 -512.88917576 -0.00089050 -0.00058603 0.27D-05 0.82D-06 14.09 4 1 1 1.15474778 -0.54050536 -512.88922727 -0.00005151 -0.00000652 0.31D-07 0.18D-07 18.38 5 1 1 1.15475704 -0.54050823 -512.88923014 -0.00000287 -0.00000549 0.61D-09 0.25D-09 22.66 6 1 1 1.15475868 -0.54050873 -512.88923064 -0.00000050 -0.00000015 0.13D-10 0.52D-11 26.93 7 1 1 1.15475884 -0.54050877 -512.88923069 -0.00000005 -0.00000007 0.28D-12 0.14D-12 31.21 Energies without level shift correction: 7 1 1 1.15475884 -0.49408112 -512.84280303 Energy contributions for state 1.1: =================================== Energy contr. SQ.Norm of FOWF Space I -0.00426223 0.00220168 Space S -0.10724946 0.04501661 Space P -0.38256942 0.10754056 ===================================== Analysis of CPU times by interactions ===================================== I S P I 1.3% S 8.7% 6.2% P 0.3% 63.2% 2.9% Initialization: 15.2% Other: 2.1% Total CPU: 31.2 seconds ===================================== gnormi= 1.00220168 gnorms= 0.04501661 gnormp= 0.10754056 gnorm= 1.15475884 ecorri= -0.00426223 ecorrs= -0.10724946 ecorrp= -0.38256942 ecorr= -0.54050877 Reference coefficients greater than 0.0500000 ============================================= 2222222202200 0.9093104 2222222202/\0 0.2279550 2222222202020 -0.1401939 2222220222200 -0.1229192 222222220/\20 0.1204072 2222222200220 -0.1054410 222222/2\2/0\ -0.0966954 222222220/2\0 0.0960079 222222220/\/\ -0.0883384 222222/2\/20\ 0.0648328 2222222202002 -0.0584851 222222220/\02 -0.0579526 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 0.00220168 -0.00426223 0.53118327 Singles 0.04501661 -0.10724946 -0.23465489 Pairs 0.10754056 -0.38256941 -0.83703715 Total 1.15475884 -0.49408110 -0.54050877 +++++++++++++++++++++++++++++++++++++++++++++++++++ Reference energy -512.34872191 Nuclear energy 115.82702136 Kinetic energy 512.52881557 One electron energy -933.35203275 Two electron energy 304.63578071 Virial quotient -1.00070321 Correlation energy -0.54050877 !RSPT2 STATE 1.1 Energy -512.889230685842 Properties without orbital relaxation: !RSPT2 STATE 1.1 Dipole moment -0.70479966 0.00000000 -0.17853821 Dipole moment /Debye -1.79130472 0.00000000 -0.45376915 !RSPT expec <1.1|H|1.1> -512.838815732046 Correlation energy -0.56594018 !RSPT3 STATE 1.1 Energy -512.914662095383 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 972.54 500 700 610 900 950 970 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 20.08 500 610 700 1000 520 2100 2140 1001 2141 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF PROGRAMS * TOTAL RS3 MULTI INT RESTART CPU TIMES * 129.11 91.13 10.60 27.17 0.02 REAL TIME * 138.35 SEC DISK USED * 3.11 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 Singlet Number of electrons: 36 Maximum number of shells: 6 Maximum number of spin couplings: 42 Reference space: 172 conf 236 CSFs N elec internal: 5334 conf 10696 CSFs N-1 el internal: 8121 conf 28252 CSFs N-2 el internal: 6302 conf 37605 CSFs Number of electrons in valence space: 20 Maximum number of open shell orbitals in reference space: 6 Maximum number of open shell orbitals in internal spaces: 10 Number of core orbitals: 8 ( 7 1 ) Number of closed-shell orbitals: 6 ( 6 0 ) Number of active orbitals: 7 ( 3 4 ) Number of external orbitals: 213 ( 139 74 ) 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: 12 Reference wavefunction optimized for reference space (refopt=1) State Reference Energy 1 -512.27286909 Number of blocks in overlap matrix: 4 Smallest eigenvalue: 0.49D-02 Number of N-2 electron functions: 169 Number of N-1 electron functions: 28252 Number of internal configurations: 5276 Number of singly external configurations: 3014688 Number of doubly external configurations: 1944631 Total number of contracted configurations: 4964595 Total number of uncontracted configurations: 454892214 Weight factors for SA-density in H0: 1.000000 FIMAX= 0.42D-01 FXMAX= 0.10D-01 DIAG= F F NOREF=1 NOINT=0 IHPPD=2 Nuclear energy: 115.82702136 Core energy: -559.20890571 Zeroth-order valence energy: -12.54163865 Zeroth-order total energy: -455.92352300 First-order energy: -56.34934608 Diagonal Coupling coefficients finished. Storage: 2163475 words, CPU-Time: 0.11 seconds. Energy denominators for pairs finished in 0 passes. Storage: 344059 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 1.04960497 -0.01488149 -512.28775058 -0.01488149 -0.49695957 0.50D-01 0.11D+00 1.10 2 1 1 1.16033180 -0.54766891 -512.82053800 -0.53278742 -0.00056306 0.21D-03 0.18D-03 5.42 3 1 1 1.16085613 -0.54875671 -512.82162579 -0.00108780 -0.00061437 0.34D-05 0.11D-05 9.74 4 1 1 1.16104189 -0.54882211 -512.82169119 -0.00006540 -0.00000681 0.44D-07 0.29D-07 14.06 5 1 1 1.16105428 -0.54882596 -512.82169504 -0.00000385 -0.00000632 0.13D-08 0.42D-09 18.38 6 1 1 1.16105653 -0.54882663 -512.82169572 -0.00000068 -0.00000017 0.30D-10 0.16D-10 22.69 7 1 1 1.16105678 -0.54882671 -512.82169579 -0.00000007 -0.00000009 0.12D-11 0.39D-12 27.00 Energies without level shift correction: 7 1 1 1.16105678 -0.50050967 -512.77337876 Energy contributions for state 1.2: =================================== Energy contr. SQ.Norm of FOWF Space I -0.00338525 0.00180268 Space S -0.11277282 0.05014097 Space P -0.38435160 0.10911314 ===================================== Analysis of CPU times by interactions ===================================== I S P I 1.5% S 10.4% 7.4% P 0.3% 73.2% 3.4% Initialization: 1.3% Other: 2.5% Total CPU: 27.0 seconds ===================================== gnormi= 1.00180268 gnorms= 0.05014097 gnormp= 0.10911314 gnorm= 1.16105678 ecorri= -0.00338525 ecorrs= -0.11277282 ecorrp= -0.38435160 ecorr= -0.54882671 Reference coefficients greater than 0.0500000 ============================================= 2222222/022\0 0.9305250 2222222/02\20 0.1849125 2222222/0\220 0.1506389 2222220/222\0 -0.1275260 2222222/0\2/\ -0.0931973 222222//\2/\\ -0.0641029 2222222/0220\ -0.0583135 2222222/0/\\2 -0.0536372 2222222/002\2 -0.0530592 2222222/020\2 -0.0518883 222222/2022\0 0.0514276 222222//\/2\\ 0.0510499 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 0.00180268 -0.00338524 0.54140260 Singles 0.05014097 -0.11277281 -0.24731883 Pairs 0.10911314 -0.38435160 -0.84291048 Total 1.16105678 -0.50050965 -0.54882671 +++++++++++++++++++++++++++++++++++++++++++++++++++ Reference energy -512.27286909 Nuclear energy 115.82702136 Kinetic energy 512.65123694 One electron energy -933.10148738 Two electron energy 304.45277023 Virial quotient -1.00033250 Correlation energy -0.54882671 !RSPT2 STATE 1.2 Energy -512.821695791063 Properties without orbital relaxation: !RSPT2 STATE 1.2 Dipole moment -0.26219954 0.00000000 -0.19419421 Dipole moment /Debye -0.66640111 0.00000000 -0.49356011 !RSPT expec <1.2|H|1.2> -512.762409804826 Correlation energy -0.56838459 !RSPT3 STATE 1.2 Energy -512.841253673836 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 972.54 500 700 610 900 950 970 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 20.08 500 610 700 1000 520 2100 2140 1001 2141 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF PROGRAMS * TOTAL RS3 RS3 MULTI INT RESTART CPU TIMES * 216.38 87.27 91.13 10.60 27.17 0.02 REAL TIME * 227.38 SEC DISK USED * 3.11 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: 6 Maximum number of spin couplings: 42 Reference space: 185 conf 254 CSFs N elec internal: 5334 conf 10696 CSFs N-1 el internal: 8121 conf 28252 CSFs N-2 el internal: 6600 conf 37750 CSFs Number of electrons in valence space: 20 Maximum number of open shell orbitals in reference space: 6 Maximum number of open shell orbitals in internal spaces: 10 Number of core orbitals: 8 ( 7 1 ) Number of closed-shell orbitals: 6 ( 6 0 ) Number of active orbitals: 7 ( 3 4 ) Number of external orbitals: 213 ( 139 74 ) 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: 12 Reference wavefunction optimized for reference space (refopt=1) State Reference Energy 1 -512.34872191 Number of blocks in overlap matrix: 4 Smallest eigenvalue: 0.19D-02 Number of N-2 electron functions: 169 Number of N-1 electron functions: 28252 Number of internal configurations: 5420 Number of singly external configurations: 3002988 Number of doubly external configurations: 1944631 Total number of contracted configurations: 4953039 Total number of uncontracted configurations: 456820436 Weight factors for SA-density in H0: 1.000000 FIMAX= 0.42D-01 FXMAX= 0.10D-01 DIAG= F F NOREF=1 NOINT=0 IHPPD=2 Nuclear energy: 115.82702136 Core energy: -559.20890571 Zeroth-order valence energy: -8.06968294 Zeroth-order total energy: -451.45156729 First-order energy: -60.89715463 Diagonal Coupling coefficients finished. Storage: 2172341 words, CPU-Time: 0.11 seconds. Energy denominators for pairs finished in 0 passes. Storage: 344452 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 1.04122730 -0.01236819 -512.36109010 -0.01236819 -0.48531016 0.41D-01 0.11D+00 1.13 2 1 1 1.14982652 -0.53356012 -512.88228203 -0.52119193 -0.00042726 0.14D-03 0.15D-03 5.42 3 1 1 1.14991925 -0.53438392 -512.88310583 -0.00082380 -0.00054433 0.22D-05 0.74D-06 9.70 4 1 1 1.15005741 -0.53443267 -512.88315459 -0.00004875 -0.00000821 0.22D-07 0.15D-07 13.98 5 1 1 1.15006565 -0.53443523 -512.88315714 -0.00000255 -0.00000487 0.43D-09 0.21D-09 18.26 6 1 1 1.15006715 -0.53443568 -512.88315760 -0.00000045 -0.00000016 0.82D-11 0.42D-11 22.54 7 1 1 1.15006729 -0.53443572 -512.88315763 -0.00000004 -0.00000006 0.18D-12 0.10D-12 26.83 Energies without level shift correction: 7 1 1 1.15006729 -0.48941553 -512.83813745 Energy contributions for state 1.1: =================================== Energy contr. SQ.Norm of FOWF Space I -0.00410512 0.00200754 Space S -0.10432059 0.04175968 Space P -0.38098983 0.10630008 ===================================== Analysis of CPU times by interactions ===================================== I S P I 1.6% S 10.1% 7.3% P 0.3% 73.5% 3.4% Initialization: 1.3% Other: 2.4% Total CPU: 26.8 seconds ===================================== gnormi= 1.00200754 gnorms= 0.04175968 gnormp= 0.10630008 gnorm= 1.15006729 ecorri= -0.00410512 ecorrs= -0.10432059 ecorrp= -0.38098983 ecorr= -0.53443572 Reference coefficients greater than 0.0500000 ============================================= 2222222202200 0.9093104 2222222202/\0 0.2279550 2222222202020 -0.1401939 2222220222200 -0.1229192 222222220/\20 0.1204072 2222222200220 -0.1054410 222222/2\2/0\ -0.0966954 222222220/2\0 0.0960079 222222220/\/\ -0.0883384 222222/2\/20\ 0.0648328 2222222202002 -0.0584851 222222220/\02 -0.0579526 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 0.00200754 -0.00410512 0.52547023 Singles 0.04175968 -0.10432058 -0.22783358 Pairs 0.10630008 -0.38098982 -0.83207237 Total 1.15006729 -0.48941552 -0.53443572 +++++++++++++++++++++++++++++++++++++++++++++++++++ Reference energy -512.34872191 Nuclear energy 115.82702136 Kinetic energy 512.53181519 One electron energy -933.36973792 Two electron energy 304.65955893 Virial quotient -1.00068550 Correlation energy -0.53443572 !RSPT2 STATE 1.1 Energy -512.883157634159 Properties without orbital relaxation: !RSPT2 STATE 1.1 Dipole moment -0.71357302 0.00000000 -0.18351121 Dipole moment /Debye -1.81360292 0.00000000 -0.46640842 !RSPT expec <1.1|H|1.1> -512.840154977674 Correlation energy -0.56518110 !RSPT3 STATE 1.1 Energy -512.913903016445 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 972.54 500 700 610 900 950 970 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 20.08 500 610 700 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 * 303.14 86.75 87.27 91.13 10.60 27.17 0.02 REAL TIME * 315.89 SEC DISK USED * 3.11 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 Singlet Number of electrons: 36 Maximum number of shells: 6 Maximum number of spin couplings: 42 Reference space: 172 conf 236 CSFs N elec internal: 5334 conf 10696 CSFs N-1 el internal: 8121 conf 28252 CSFs N-2 el internal: 6302 conf 37605 CSFs Number of electrons in valence space: 20 Maximum number of open shell orbitals in reference space: 6 Maximum number of open shell orbitals in internal spaces: 10 Number of core orbitals: 8 ( 7 1 ) Number of closed-shell orbitals: 6 ( 6 0 ) Number of active orbitals: 7 ( 3 4 ) Number of external orbitals: 213 ( 139 74 ) 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: 12 Reference wavefunction optimized for reference space (refopt=1) State Reference Energy 1 -512.27286909 Number of blocks in overlap matrix: 4 Smallest eigenvalue: 0.49D-02 Number of N-2 electron functions: 169 Number of N-1 electron functions: 28252 Number of internal configurations: 5276 Number of singly external configurations: 3014688 Number of doubly external configurations: 1944631 Total number of contracted configurations: 4964595 Total number of uncontracted configurations: 454892214 Weight factors for SA-density in H0: 1.000000 FIMAX= 0.42D-01 FXMAX= 0.10D-01 DIAG= F F NOREF=1 NOINT=0 IHPPD=2 Nuclear energy: 115.82702136 Core energy: -559.20890571 Zeroth-order valence energy: -7.86788597 Zeroth-order total energy: -451.24977032 First-order energy: -61.02309877 Diagonal Coupling coefficients finished. Storage: 2163475 words, CPU-Time: 0.11 seconds. Energy denominators for pairs finished in 0 passes. Storage: 344059 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 1.04227976 -0.01268393 -512.28555301 -0.01268393 -0.48641832 0.42D-01 0.11D+00 1.10 2 1 1 1.14949577 -0.53380897 -512.80667806 -0.52112504 -0.00062240 0.15D-03 0.16D-03 5.43 3 1 1 1.14986744 -0.53475179 -512.80762087 -0.00094281 -0.00054637 0.24D-05 0.84D-06 9.76 4 1 1 1.15002953 -0.53480839 -512.80767747 -0.00005660 -0.00000748 0.23D-07 0.21D-07 14.08 5 1 1 1.15003868 -0.53481123 -512.80768031 -0.00000284 -0.00000516 0.57D-09 0.26D-09 18.40 6 1 1 1.15004045 -0.53481176 -512.80768085 -0.00000053 -0.00000016 0.11D-10 0.70D-11 22.71 7 1 1 1.15004061 -0.53481181 -512.80768089 -0.00000004 -0.00000006 0.32D-12 0.16D-12 27.03 Energies without level shift correction: 7 1 1 1.15004061 -0.48979962 -512.76266871 Energy contributions for state 1.2: =================================== Energy contr. SQ.Norm of FOWF Space I -0.00318814 0.00154058 Space S -0.10659425 0.04294158 Space P -0.38001724 0.10555845 ===================================== Analysis of CPU times by interactions ===================================== I S P I 1.5% S 10.6% 7.4% P 0.4% 73.2% 3.3% Initialization: 1.3% Other: 2.4% Total CPU: 27.0 seconds ===================================== gnormi= 1.00154058 gnorms= 0.04294158 gnormp= 0.10555845 gnorm= 1.15004061 ecorri= -0.00318814 ecorrs= -0.10659425 ecorrp= -0.38001724 ecorr= -0.53481181 Reference coefficients greater than 0.0500000 ============================================= 2222222/022\0 0.9305250 2222222/02\20 0.1849125 2222222/0\220 0.1506389 2222220/222\0 -0.1275260 2222222/0\2/\ -0.0931973 222222//\2/\\ -0.0641029 2222222/0220\ -0.0583135 2222222/0/\\2 -0.0536372 2222222/002\2 -0.0530592 2222222/020\2 -0.0518883 222222/2022\0 0.0514276 222222//\/2\\ 0.0510499 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 0.00154058 -0.00318814 0.52784953 Singles 0.04294158 -0.10659424 -0.23278033 Pairs 0.10555845 -0.38001723 -0.82988101 Total 1.15004061 -0.48979961 -0.53481181 +++++++++++++++++++++++++++++++++++++++++++++++++++ Reference energy -512.27286909 Nuclear energy 115.82702136 Kinetic energy 512.64141417 One electron energy -933.09932680 Two electron energy 304.46462455 Virial quotient -1.00032433 Correlation energy -0.53481181 !RSPT2 STATE 1.2 Energy -512.807680890882 Properties without orbital relaxation: !RSPT2 STATE 1.2 Dipole moment -0.25282575 0.00000000 -0.18957548 Dipole moment /Debye -0.64257686 0.00000000 -0.48182125 !RSPT expec <1.2|H|1.2> -512.764626326803 Correlation energy -0.56554081 !RSPT3 STATE 1.2 Energy -512.838409892222 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 972.54 500 700 610 900 950 970 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 20.08 500 610 700 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 * 390.39 87.25 86.75 87.27 91.13 10.60 27.17 0.02 REAL TIME * 404.91 SEC DISK USED * 3.11 GB ********************************************************************************************************************************** RS3/aug-cc-pVTZ energy= -512.838409892222 RS3 RS3 RS3 RS3 MULTI -512.83840989 -512.91390302 -512.84125367 -512.91466210 -512.27286909 ********************************************************************************************************************************** Molpro calculation terminated