Working directory : /state/partition1/1196085/molpro.Y7UqnNxfNt/ Global scratch directory : /state/partition1/1196085/molpro.Y7UqnNxfNt/ Wavefunction directory : /home/boggio/wfu/ Main file repository : /state/partition1/1196085/molpro.Y7UqnNxfNt/ id : irsamc Nodes nprocs compute-14-5.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 ***,tetrazine, CASPT3(14,10)/aug-cc-pVTZ 1Ag,1B1g,2B1g calculation memory,2000,m file,2,tetra_sa3cas10_avtz_b1g.wfu GEOMTYP=xyz GEOMETRY={ 8 CC3/aug-cc-pVTZ S0 optimised geometry C 0.0000000000 0.0000000000 1.2605433161 C 0.0000000000 0.0000000000 -1.2605433161 N 0.0000000000 1.1942113802 0.6613300177 N 0.0000000000 -1.1942113802 0.6613300177 N 0.0000000000 1.1942113802 -0.6613300177 N 0.0000000000 -1.1942113802 -0.6613300177 H 0.0000000000 0.0000000000 2.3381742738 H 0.0000000000 0.0000000000 -2.3381742738} BASIS=AVTZ INT {MULTI occ,6,2,4,1,5,2,3,1 closed,5,0,3,0,4,0,2,0 wf,42,1,0 wf,42,4,0 state,2 canonical print,orbitals,civector} {RS3,shift=0.4 wf,42,1,0} {RS3,shift=0.4 wf,42,4,0} {RS3,shift=0.4 wf,42,4,0 state,1,2} {RS3,shift=0.4,ipea=0.25 wf,42,1,0} {RS3,shift=0.4,ipea=0.25 wf,42,4,0} {RS3,shift=0.4,ipea=0.25 wf,42,4,0 state,1,2} 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 * tetrazine, CASPT3(14,10)/aug-cc-pVTZ 1Ag,1B1g,2B1g calculation 64 bit serial version DATE: 23-Jan-22 TIME: 22:29:12 ********************************************************************************************************************************** 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 tetra_sa3cas10_avtz_b1g.wfu assigned. Implementation=df Size= 19.59 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 _NELEC = 42.00000000 _PROGRAM = MULTI _DMX(2:3) = 0.00000000 0.00000000 _DMY(2:3) = 0.00000000 0.00000000 _DMZ(2:3) = 0.00000000 0.00000000 _DMX_SCF = 0.00000000 _DMY_SCF = 0.00000000 _DMZ_SCF = 0.00000000 _HOMO = 3.70000000 _EHOMO = -0.41619490 _LUMO = 1.80000000 _ELUMO = 0.03523420 _ENERGY(1:3) = -294.78883369 -294.59102642 -294.52487275 _ENERGY_METHOD = MULTI _ENERGY_BASIS = aug-cc-pVTZ _ENUC = 212.85767471 _IPROC_MPP = 0.00000000 _IPROC_MPPX = 0.00000000 _ORBITAL = 2141.20000000 _STATUS = 1.00000000 _VERSION = 0.20190010D+07 _DATE = 15-Nov-19 _LASTORB = MCSCF _MACHINE = 64 bit serial version _OUTPUT = /home/boggio/TETRAZINE/molpro.xml _PGROUP = D2h _TIME = 16:23:16 _LIBMOL = /home/thierry/PROGRAMS/Molpro2018/Molpro_release/lib/ _DMX_CC(1:3) = -0.00000000 -0.00000000 -0.00000000 _DMY_CC(1:3) = -0.00000000 -0.00000000 -0.00000000 _DMZ_CC(1:3) = -0.00000000 -0.00000000 -0.00000000 _DMX_NUC(1:3) = 0.00000000 0.00000000 0.00000000 _DMY_NUC(1:3) = 0.00000000 0.00000000 0.00000000 _DMZ_NUC(1:3) = 0.00000000 0.00000000 0.00000000 _TRDMX(1:3) = -0.00000000 -0.00000000 -0.00000000 _TRDMY(1:3) = -0.00000000 -0.00000000 -0.00000000 _TRDMZ(1:3) = -0.00000000 -0.00000000 -0.00000000 Geometry written to block 1 of record 700 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 2 9 19.59 500 610 700 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 * 0.18 SEC DISK USED * 31.07 MB ********************************************************************************************************************************** SETTING GEOMTYP = XYZ 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 D2h ATOMIC COORDINATES NR ATOM CHARGE X Y Z 1 C 6.00 0.000000000 0.000000000 2.382081636 2 C 6.00 0.000000000 0.000000000 -2.382081636 3 N 7.00 0.000000000 2.256732443 1.249732611 4 N 7.00 0.000000000 -2.256732443 1.249732611 5 N 7.00 0.000000000 2.256732443 -1.249732611 6 N 7.00 0.000000000 -2.256732443 -1.249732611 7 H 1.00 0.000000000 0.000000000 4.418509009 8 H 1.00 0.000000000 0.000000000 -4.418509009 Bond lengths in Bohr (Angstrom) 1-3 2.524887252 1-4 2.524887252 1-7 2.036427373 2-5 2.524887252 2-6 2.524887252 ( 1.336112794) ( 1.336112794) ( 1.077630958) ( 1.336112794) ( 1.336112794) 2-8 2.036427373 3-5 2.499465223 4-6 2.499465223 ( 1.077630958) ( 1.322660035) ( 1.322660035) Bond angles 1-3-5 116.64588899 1-4-6 116.64588899 2-5-3 116.64588899 2-6-4 116.64588899 3-1-4 126.70822202 3-1-7 116.64588899 4-1-7 116.64588899 5-2-6 126.70822202 5-2-8 116.64588899 6-2-8 116.64588899 NUCLEAR CHARGE: 42 NUMBER OF PRIMITIVE AOS: 456 NUMBER OF SYMMETRY AOS: 398 NUMBER OF CONTRACTIONS: 322 ( 60Ag + 32B3u + 46B2u + 23B1g + 60B1u + 32B2g + 46B3g + 23Au ) NUMBER OF INNER CORE ORBITALS: 0 ( 0Ag + 0B3u + 0B2u + 0B1g + 0B1u + 0B2g + 0B3g + 0Au ) NUMBER OF OUTER CORE ORBITALS: 6 ( 2Ag + 0B3u + 1B2u + 0B1g + 2B1u + 0B2g + 1B3g + 0Au ) NUMBER OF VALENCE ORBITALS: 26 ( 6Ag + 2B3u + 4B2u + 1B1g + 6B1u + 2B2g + 4B3g + 1Au ) NUCLEAR REPULSION ENERGY 212.85767471 Eigenvalues of metric 1 0.534E-04 0.126E-03 0.489E-03 0.757E-03 0.108E-02 0.138E-02 0.200E-02 0.250E-02 2 0.295E-02 0.656E-02 0.110E-01 0.170E-01 0.293E-01 0.367E-01 0.495E-01 0.740E-01 3 0.232E-03 0.731E-03 0.117E-02 0.220E-02 0.243E-02 0.300E-02 0.383E-02 0.775E-02 4 0.450E-02 0.204E-01 0.418E-01 0.563E-01 0.108E+00 0.147E+00 0.171E+00 0.251E+00 5 0.153E-04 0.204E-04 0.317E-04 0.414E-04 0.105E-03 0.405E-03 0.645E-03 0.915E-03 6 0.803E-03 0.222E-02 0.351E-02 0.527E-02 0.785E-02 0.141E-01 0.205E-01 0.232E-01 7 0.202E-04 0.252E-04 0.149E-03 0.351E-03 0.428E-03 0.114E-02 0.184E-02 0.250E-02 8 0.181E-02 0.238E-02 0.107E-01 0.144E-01 0.255E-01 0.404E-01 0.539E-01 0.851E-01 Contracted 2-electron integrals neglected if value below 1.0D-12 AO integral compression algorithm 1 Integral accuracy 1.0D-12 1286.341 MB (compressed) written to integral file ( 64.6%) NUMBER OF SORTED TWO-ELECTRON INTEGRALS: 172927595. BUFFER LENGTH: 32768 NUMBER OF SEGMENTS: 6 SEGMENT LENGTH: 31999362 RECORD LENGTH: 524288 Memory used in sort: 32.56 MW SORT1 READ 248995728. AND WROTE 171947226. INTEGRALS IN 496 RECORDS. CPU TIME: 7.59 SEC, REAL TIME: 9.09 SEC SORT2 READ 171947226. AND WROTE 172927595. INTEGRALS IN 4907 RECORDS. CPU TIME: 2.70 SEC, REAL TIME: 3.32 SEC FILE SIZES: FILE 1: 1318.8 MBYTE, FILE 4: 2080.4 MBYTE, TOTAL: 3399.2 MBYTE OPERATOR DM FOR CENTER 0 COORDINATES: 0.000000 0.000000 0.000000 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 19 922.65 500 700 610 900 950 970 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 19.59 500 610 700 1000 520 2100 2140 1001 2141 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF PROGRAMS * TOTAL INT RESTART CPU TIMES * 24.95 24.83 0.01 REAL TIME * 28.29 SEC DISK USED * 3.19 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 ( 5 0 3 0 4 0 2 0 ) Number of active orbitals: 10 ( 1 2 1 1 1 2 1 1 ) Number of external orbitals: 298 ( 54 30 42 22 55 30 43 22 ) State symmetry 1 Number of active electrons: 14 Spin symmetry=Singlet Space symmetry=1 Number of states: 1 Number of CSFs: 670 (1824 determinants, 14400 intermediate states) State symmetry 2 Number of active electrons: 14 Spin symmetry=Singlet Space symmetry=4 Number of states: 2 Number of CSFs: 610 (1792 determinants, 14400 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: 0.33333 Weight factors for state symmetry 2: 0.33333 0.33333 Number of orbital rotations: 1074 ( 14 closed/active, 702 closed/virtual, 0 active/active, 358 active/virtual ) Total number of variables: 6482 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 8 49 0 -294.63491095 -294.63491095 -0.00000000 0.00002017 0.00000001 0.00000003 0.54E-07 2.04 CONVERGENCE REACHED! Final gradient: 0.00000002 ( 0.19E-07) Final energy: -294.63491095 Molecular orbital coefficients: Orbital Occupation Energy Cen Mu Typ Coefficients 1.1 2.00000 0.00000 3 1 s 0.99924 2.1 2.00000 0.00000 1 1 s 1.00038 3.1 2.00000 0.00000 1 2 s 0.41636 3 2 s 0.74848 4.1 2.00000 0.00000 1 2 s 0.64074 3 1 pz 0.60955 7 1 s 0.38524 5.1 2.00000 0.00000 1 1 pz 0.63941 3 1 py 0.30293 3 1 pz -0.46224 7 1 s 0.71087 7 3 s -0.37670 6.1 1.00000 0.00000 3 2 s 0.47228 3 1 py 0.57203 3 1 pz 0.51060 1.2 1.00000 0.00000 1 1 px 0.45888 3 1 px 0.67768 2.2 1.00000 0.00000 1 1 px 0.87797 3 1 px -0.71994 1.3 2.00000 0.00000 3 1 s 0.99926 2.3 2.00000 0.00000 1 1 py 0.25936 3 2 s 0.87285 3 1 pz -0.26479 3.3 2.00000 0.00000 1 1 py 0.54602 3 1 py -0.31084 3 1 pz 0.76931 4.3 1.00000 0.00000 3 2 s 0.26325 3 1 py 0.79144 3 1 pz 0.39010 1.4 1.00000 0.00000 3 1 px 0.87992 1.5 2.00000 0.00000 3 1 s 0.99919 2.5 2.00000 0.00000 1 1 s 1.00079 3.5 2.00000 0.00000 1 2 s 0.68782 3 2 s 0.62624 4.5 2.00000 0.00000 1 2 s 0.26808 1 1 pz 0.65304 3 2 s -0.38679 7 1 s 0.78443 7 3 s -0.44896 5.5 1.00000 0.00000 1 2 s -0.41543 1 1 pz 0.28735 3 2 s 0.54774 3 4 s 0.32662 3 5 s 0.57483 3 1 py 0.71000 1.6 1.00000 0.00000 1 1 px 0.68686 3 1 px 0.58775 2.6 1.00000 0.00000 1 1 px -0.74150 3 1 px 1.01653 1.7 2.00000 0.00000 3 1 s 0.99836 2.7 2.00000 0.00000 1 1 py 0.53005 3 2 s 0.78468 3 1 pz 0.29516 3 3 pz -0.27829 3.7 1.00000 0.00000 1 1 py -0.45839 3 2 s 0.41622 3 5 s 0.32430 3 1 py 0.87066 1.8 1.00000 0.00000 3 1 px 1.03610 CI Coefficients of symmetry 1 ============================= 2 20 2 2 2 20 2 0 0.92242244 2 20 2 0 2 20 2 2 -0.17742545 2 22 2 2 2 00 2 0 -0.13290199 2 2a 2 b 2 a0 2 b 0.11250556 2 2b 2 a 2 b0 2 a 0.11250556 2 2b 2 a 2 a0 2 b -0.08043834 2 2a 2 b 2 b0 2 a -0.08043834 2 a0 2 b 2 2a 2 b 0.07616869 2 b0 2 a 2 2b 2 a 0.07616869 2 ba 2 2 2 ab 2 0 -0.06657436 2 ab 2 2 2 ba 2 0 -0.06657436 2 20 2 2 2 00 2 2 -0.05687996 2 b0 2 a 2 2a 2 b -0.05453845 2 a0 2 b 2 2b 2 a -0.05453845 Energy: -294.78883369 CI Coefficients of symmetry 4 ============================= 2 20 2 2 a 20 2 b 0.58466397 0.05295701 2 20 2 2 b 20 2 a -0.58466397 -0.05295701 2 20 2 2 2 b0 a 2 0.13396047 -0.45428087 2 20 2 2 2 a0 b 2 -0.13396047 0.45428087 2 20 2 2 2 2b a 0 -0.08328972 -0.34189019 2 20 2 2 2 2a b 0 0.08328972 0.34189019 2 2a 2 b 2 20 a b -0.16035542 0.03311598 2 2b 2 a 2 20 b a -0.16035542 0.03311598 2 2b 2 b 2 20 a a 0.08153439 -0.15970098 2 2a 2 a 2 20 b b 0.08153439 -0.15970098 a 20 2 b 2 20 2 2 -0.14920242 -0.04178885 b 20 2 a 2 20 2 2 0.14920242 0.04178885 2 2b 2 a 2 20 a b 0.07882104 0.12658499 2 2a 2 b 2 20 b a 0.07882104 0.12658499 2 22 2 2 2 b0 a 0 0.05024916 0.12009997 2 22 2 2 2 a0 b 0 -0.05024916 -0.12009997 2 b0 a 2 2 20 2 2 0.02543638 0.11798982 2 a0 b 2 2 20 2 2 -0.02543638 -0.11798982 2 2b a 2 2 20 2 0 0.07779686 -0.09059877 2 2a b 2 2 20 2 0 -0.07779686 0.09059877 2 20 a b 2 2a 2 b -0.07871066 -0.01960017 2 20 b a 2 2b 2 a -0.07871066 -0.01960017 2 ab 2 2 2 b0 a 2 0.00427204 -0.07668801 2 ba 2 2 2 a0 b 2 0.00427204 -0.07668801 2 bb 2 2 2 a0 a 2 -0.01178209 0.07272127 2 aa 2 2 2 b0 b 2 -0.01178209 0.07272127 2 22 2 2 a 00 2 b -0.07008730 -0.04560230 2 22 2 2 b 00 2 a 0.07008730 0.04560230 2 20 2 2 2 0b a 2 -0.00582641 0.06957230 2 20 2 2 2 0a b 2 0.00582641 -0.06957230 2 20 2 2 a ba 2 b 0.01977929 0.06636305 2 20 2 2 b ab 2 a 0.01977929 0.06636305 2 20 a b 2 2b 2 a 0.03553015 0.06505423 2 20 b a 2 2a 2 b 0.03553015 0.06505423 2 2b 2 a a 2b 2 0 -0.01971508 0.06442277 2 2a 2 b b 2a 2 0 -0.01971508 0.06442277 2 2a 2 b a b0 2 2 -0.01948759 -0.05756941 2 2b 2 a b a0 2 2 -0.01948759 -0.05756941 2 bb 2 2 a 20 2 a 0.05683967 -0.03830222 2 aa 2 2 b 20 2 b 0.05683967 -0.03830222 2 2b 2 a a b0 2 2 0.03155935 0.05655134 2 2a 2 b b a0 2 2 0.03155935 0.05655134 2 20 2 2 2 b2 a 0 -0.02676531 0.05415554 2 20 2 2 2 a2 b 0 0.02676531 -0.05415554 2 20 2 2 a bb 2 a -0.05327673 -0.02490254 2 20 2 2 b aa 2 b -0.05327673 -0.02490254 2 2b 2 a 2 ba a b 0.00574230 -0.05141529 2 2a 2 b 2 ab b a -0.00574230 0.05141529 Energy: -294.59102642 -294.52487275 Results for state 1.1 ===================== !MCSCF STATE 1.1 Energy -294.788833690513 Nuclear energy 212.85767471 Kinetic energy 294.27977719 One electron energy -820.80493036 Two electron energy 313.15842196 Virial ratio 2.00172984 !MCSCF STATE 1.1 Dipole moment 0.00000000 0.00000000 0.00000000 Dipole moment /Debye 0.00000000 0.00000000 0.00000000 Results for state 1.4 ===================== !MCSCF STATE 1.4 Energy -294.591026420267 Nuclear energy 212.85767471 Kinetic energy 294.36037502 One electron energy -821.05885506 Two electron energy 313.61015393 Virial ratio 2.00078357 !MCSCF STATE 1.4 Dipole moment 0.00000000 0.00000000 0.00000000 Dipole moment /Debye 0.00000000 0.00000000 0.00000000 Results for state 2.4 ===================== !MCSCF STATE 2.4 Energy -294.524872749631 Nuclear energy 212.85767471 Kinetic energy 294.76602922 One electron energy -821.11223946 Two electron energy 313.72969200 Virial ratio 1.99918187 !MCSCF STATE 2.4 Dipole moment 0.00000000 0.00000000 0.00000000 Dipole moment /Debye 0.00000000 0.00000000 0.00000000 State-averaged charge density matrix saved on record 2141.2 (density set 1) No non-zero expectation values PSEUDO CANONICAL ORBITALS (STATE AVERAGED) ========================================== Orbital Occupation Energy Cen Mu Typ Coefficients 1.1 2.00000 -15.63862 3 1 s 0.99924 2.1 2.00000 -11.33387 1 1 s 1.00038 3.1 2.00000 -1.42471 1 2 s 0.41636 3 2 s 0.74848 4.1 2.00000 -0.93535 1 2 s 0.64074 3 1 pz 0.60955 7 1 s 0.38524 5.1 2.00000 -0.64888 1 1 pz 0.63941 3 1 py 0.30293 3 1 pz -0.46224 7 1 s 0.71087 7 3 s -0.37670 6.1 1.97100 -0.61347 3 2 s 0.47228 3 1 py 0.57203 3 1 pz 0.51060 1.2 1.93221 -0.63021 1 1 px 0.43650 3 1 px 0.69569 2.2 0.20700 0.08846 1 1 px 0.88931 3 1 px -0.70255 1.3 2.00000 -15.63866 3 1 s 0.99926 2.3 2.00000 -1.31865 1 1 py 0.25936 3 2 s 0.87285 3 1 pz -0.26479 3.3 2.00000 -0.77271 1 1 py 0.54602 3 1 py -0.31084 3 1 pz 0.76931 4.3 1.96167 -0.54655 3 2 s 0.26325 3 1 py 0.79144 3 1 pz 0.39010 1.4 1.82721 -0.48324 3 1 px 0.87992 1.5 2.00000 -15.63781 3 1 s 0.99919 2.5 2.00000 -11.33389 1 1 s 1.00079 3.5 2.00000 -1.17787 1 2 s 0.68782 3 2 s 0.62624 4.5 2.00000 -0.69211 1 2 s 0.26808 1 1 pz 0.65304 3 2 s -0.38679 7 1 s 0.78443 7 3 s -0.44896 5.5 1.72816 -0.47058 1 2 s -0.41543 1 1 pz 0.28735 3 2 s 0.54774 3 4 s 0.32662 3 5 s 0.57483 3 1 py 0.71000 1.6 1.72642 -0.41092 1 1 px 0.68319 3 1 px 0.59277 2.6 0.17970 0.27124 1 1 px -0.74489 3 1 px 1.01361 1.7 2.00000 -15.63783 3 1 s 0.99836 2.7 2.00000 -1.01327 1 1 py 0.53005 3 2 s 0.78468 3 1 pz 0.29516 3 3 pz -0.27829 3.7 1.66489 -0.34913 1 1 py -0.45839 3 2 s 0.41622 3 5 s 0.32430 3 1 py 0.87066 1.8 0.80174 -0.07725 3 1 px 1.03610 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 ============================= 2 20 2 2 2 20 2 0 0.92203329 2 20 2 0 2 20 2 2 -0.17690598 2 22 2 2 2 00 2 0 -0.13290199 2 2a 2 b 2 a0 2 b 0.11264130 2 2b 2 a 2 b0 2 a 0.11264130 2 2b 2 a 2 a0 2 b -0.08046911 2 2a 2 b 2 b0 2 a -0.08046911 2 a0 2 b 2 2a 2 b 0.07603553 2 b0 2 a 2 2b 2 a 0.07603553 2 ba 2 2 2 ab 2 0 -0.06599649 2 ab 2 2 2 ba 2 0 -0.06599649 2 20 2 2 2 00 2 2 -0.05729741 2 b0 2 a 2 2a 2 b -0.05450239 2 a0 2 b 2 2b 2 a -0.05450239 Energy: -294.78883369 CI Coefficients of symmetry 4 ============================= 2 20 2 2 a 20 2 b 0.58380255 0.05338479 2 20 2 2 b 20 2 a -0.58380255 -0.05338479 2 20 2 2 2 b0 a 2 0.13391998 -0.45158143 2 20 2 2 2 a0 b 2 -0.13391998 0.45158143 2 20 2 2 2 2b a 0 -0.08425181 -0.34290972 2 20 2 2 2 2a b 0 0.08425181 0.34290972 2 2a 2 b 2 20 a b -0.16122435 0.03332093 2 2b 2 a 2 20 b a -0.16122435 0.03332093 2 2b 2 b 2 20 a a 0.08205837 -0.16034849 2 2a 2 a 2 20 b b 0.08205837 -0.16034849 a 20 2 b 2 20 2 2 -0.14859597 -0.04160328 b 20 2 a 2 20 2 2 0.14859597 0.04160328 2 2b 2 a 2 20 a b 0.07916598 0.12702756 2 2a 2 b 2 20 b a 0.07916598 0.12702756 2 22 2 2 2 b0 a 0 0.05034737 0.12026158 2 22 2 2 2 a0 b 0 -0.05034737 -0.12026158 2 b0 a 2 2 20 2 2 0.02557814 0.11734264 2 a0 b 2 2 20 2 2 -0.02557814 -0.11734264 2 2b a 2 2 20 2 0 0.07796157 -0.09115986 2 2a b 2 2 20 2 0 -0.07796157 0.09115986 2 ab 2 2 2 b0 a 2 0.00789611 -0.08872479 2 ba 2 2 2 a0 b 2 0.00789611 -0.08872479 2 20 a b 2 2a 2 b -0.07878977 -0.01976182 2 20 b a 2 2b 2 a -0.07878977 -0.01976182 2 bb 2 2 2 a0 a 2 -0.01176109 0.07262967 2 aa 2 2 2 b0 b 2 -0.01176109 0.07262967 2 20 2 2 2 0b a 2 -0.00649302 0.07221696 2 20 2 2 2 0a b 2 0.00649302 -0.07221696 2 22 2 2 a 00 2 b -0.07008731 -0.04560230 2 22 2 2 b 00 2 a 0.07008731 0.04560230 2 20 2 2 a ba 2 b 0.02386847 0.06693169 2 20 2 2 b ab 2 a 0.02386847 0.06693169 2 20 a b 2 2b 2 a 0.03566212 0.06534374 2 20 b a 2 2a 2 b 0.03566212 0.06534374 2 2b 2 a a 2b 2 0 -0.01986394 0.06495750 2 2a 2 b b 2a 2 0 -0.01986394 0.06495750 2 2a 2 b a b0 2 2 -0.01948227 -0.05753465 2 2b 2 a b a0 2 2 -0.01948227 -0.05753465 2 bb 2 2 a 20 2 a 0.05686110 -0.03833697 2 aa 2 2 b 20 2 b 0.05686110 -0.03833697 2 2b 2 a a b0 2 2 0.03145515 0.05675772 2 2a 2 b b a0 2 2 0.03145515 0.05675772 2 ba 2 2 a 20 2 b -0.05429111 0.03754189 2 ab 2 2 b 20 2 a -0.05429111 0.03754189 2 20 2 2 a bb 2 a -0.05307566 -0.02489483 2 20 2 2 b aa 2 b -0.05307566 -0.02489483 2 20 2 2 2 b2 a 0 -0.02754097 0.05167543 2 20 2 2 2 a2 b 0 0.02754097 -0.05167543 2 2b 2 a 2 ba a b 0.00629937 -0.05068667 2 2a 2 b 2 ab b a -0.00629937 0.05068667 Energy: -294.59102642 -294.52487275 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 968.81 500 700 610 900 950 970 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 19.59 500 610 700 1000 520 2100 2140 1001 2141 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF PROGRAMS * TOTAL MULTI INT RESTART CPU TIMES * 28.49 3.54 24.83 0.01 REAL TIME * 32.25 SEC DISK USED * 3.19 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= 0.40 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: 42 Maximum number of shells: 6 Maximum number of spin couplings: 42 Reference space: 390 conf 670 CSFs N elec internal: 36606 conf 88770 CSFs N-1 el internal: 76788 conf 358740 CSFs N-2 el internal: 44177 conf 350834 CSFs Number of electrons in valence space: 30 Maximum number of open shell orbitals in reference space: 6 Maximum number of open shell orbitals in internal spaces: 10 Number of core orbitals: 6 ( 2 0 1 0 2 0 1 0 ) Number of closed-shell orbitals: 8 ( 3 0 2 0 2 0 1 0 ) Number of active orbitals: 10 ( 1 2 1 1 1 2 1 1 ) Number of external orbitals: 298 ( 54 30 42 22 55 30 43 22 ) Molecular orbitals read from record 2141.2 Type=MCSCF/CANONICAL (state averaged) Integral transformation finished. Total CPU: 1.17 sec, npass= 1 Memory used: 2.46 MW Number of p-space configurations: 2 Reference wavefunction optimized for reference space (refopt=1) State Reference Energy 1 -294.78883369 Number of blocks in overlap matrix: 16 Smallest eigenvalue: 0.57D-02 Number of N-2 electron functions: 324 Number of N-1 electron functions: 358740 Number of internal configurations: 11301 Number of singly external configurations: 13307036 Number of doubly external configurations: 1820790 Total number of contracted configurations: 15139127 Total number of uncontracted configurations: 2014158243 Weight factors for SA-density in H0: 1.000000 FIMAX= 0.11D+00 FXMAX= 0.92D-02 DIAG= F F NOREF=1 NOINT=0 IHPPD=2 Nuclear energy: 212.85767471 Core energy: -348.34609890 Zeroth-order valence energy: -23.34242932 Zeroth-order total energy: -158.83085351 First-order energy: -135.95798018 Diagonal Coupling coefficients finished. Storage:15543204 words, CPU-Time: 0.63 seconds. Energy denominators for pairs finished in 0 passes. Storage: 1001177 words, CPU-time: 0.00 seconds. A level shift of 0.40 is applied. ITER. STATE ROOT SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) TIME 1 1 1 1.06849509 -0.02739804 -294.81623173 -0.02739804 -0.90716075 0.68D-01 0.16D+00 4.94 2 1 1 1.22884122 -1.00187879 -295.79071248 -0.97448075 0.00044726 0.97D-04 0.99D-04 13.68 3 1 1 1.22915067 -1.00255498 -295.79138867 -0.00067619 -0.00047013 0.10D-05 0.15D-06 22.48 4 1 1 1.22918542 -1.00257147 -295.79140516 -0.00001650 0.00000021 0.68D-08 0.21D-08 31.25 5 1 1 1.22918559 -1.00257156 -295.79140525 -0.00000009 -0.00000235 0.87D-10 0.13D-10 40.02 Energies without level shift correction: 5 1 1 1.22918559 -0.91089733 -295.69973102 Energy contributions for state 1.1: =================================== Energy contr. SQ.Norm of FOWF Space I -0.00415257 0.00180014 Space S -0.18266160 0.06843645 Space P -0.72408315 0.15894900 ===================================== Analysis of CPU times by interactions ===================================== I S P I 3.6% S 16.2% 13.9% P 0.3% 56.6% 0.4% Initialization: 6.4% Other: 2.5% Total CPU: 40.0 seconds ===================================== gnormi= 1.00180014 gnorms= 0.06843645 gnormp= 0.15894900 gnorm= 1.22918559 ecorri= -0.00415257 ecorrs= -0.18266160 ecorrp= -0.72408315 ecorr= -1.00257156 Reference coefficients greater than 0.0500000 ============================================= 222220222222220220 0.9220333 22222/222\222/022\ 0.1931103 222220222022220222 -0.1769058 222222222222200220 -0.1329024 2222/0222\2222/22\ 0.1305380 2222/\2222222/\220 0.0844002 2222//2222222\\220 0.0824328 222220222222200222 -0.0572967 22222/222/222\022\ -0.0557234 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 0.00180014 -0.00415257 0.99343057 Singles 0.06843645 -0.18266160 -0.40208995 Pairs 0.15894900 -0.72408315 -1.59391219 Total 1.22918559 -0.91089732 -1.00257156 +++++++++++++++++++++++++++++++++++++++++++++++++++ Reference energy -294.78883369 Nuclear energy 212.85767471 Kinetic energy 294.95151271 One electron energy -820.47637040 Two electron energy 311.82729044 Virial quotient -1.00284756 Correlation energy -1.00257156 !RSPT2 STATE 1.1 Energy -295.791405253796 Properties without orbital relaxation: !RSPT2 STATE 1.1 Dipole moment 0.00000000 0.00000000 0.00000000 Dipole moment /Debye 0.00000000 0.00000000 0.00000000 !RSPT expec <1.1|H|1.1> -295.609220150796 Correlation energy -1.00840732 !RSPT3 STATE 1.1 Energy -295.797241006262 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 968.81 500 700 610 900 950 970 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 19.59 500 610 700 1000 520 2100 2140 1001 2141 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF PROGRAMS * TOTAL RS3 MULTI INT RESTART CPU TIMES * 539.08 510.59 3.54 24.83 0.01 REAL TIME * 548.92 SEC DISK USED * 3.19 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= 0.40 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: 4 Singlet Number of electrons: 42 Maximum number of shells: 6 Maximum number of spin couplings: 42 Reference space: 350 conf 610 CSFs N elec internal: 36606 conf 88770 CSFs N-1 el internal: 75260 conf 358244 CSFs N-2 el internal: 40780 conf 348877 CSFs Number of electrons in valence space: 30 Maximum number of open shell orbitals in reference space: 6 Maximum number of open shell orbitals in internal spaces: 10 Number of core orbitals: 6 ( 2 0 1 0 2 0 1 0 ) Number of closed-shell orbitals: 8 ( 3 0 2 0 2 0 1 0 ) Number of active orbitals: 10 ( 1 2 1 1 1 2 1 1 ) Number of external orbitals: 298 ( 54 30 42 22 55 30 43 22 ) 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: 13 Reference wavefunction optimized for reference space (refopt=1) State Reference Energy 1 -294.59102642 Number of blocks in overlap matrix: 16 Smallest eigenvalue: 0.37D-01 Number of N-2 electron functions: 324 Number of N-1 electron functions: 358244 Number of internal configurations: 11048 Number of singly external configurations: 13303514 Number of doubly external configurations: 1820790 Total number of contracted configurations: 15135352 Total number of uncontracted configurations: 2002837111 Weight factors for SA-density in H0: 1.000000 FIMAX= 0.11D+00 FXMAX= 0.35D-02 DIAG= F F NOREF=1 NOINT=0 IHPPD=2 Nuclear energy: 212.85767471 Core energy: -348.34609890 Zeroth-order valence energy: -22.28675166 Zeroth-order total energy: -157.77517586 First-order energy: -136.81585056 Diagonal Coupling coefficients finished. Storage:15286285 words, CPU-Time: 0.90 seconds. Energy denominators for pairs finished in 0 passes. Storage: 990576 words, CPU-time: 0.00 seconds. A level shift of 0.40 is applied. ITER. STATE ROOT SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) TIME 1 1 1 1.08610832 -0.03444333 -294.62546975 -0.03444333 -0.93736187 0.86D-01 0.16D+00 4.30 2 1 1 1.25089068 -1.03856908 -295.62959550 -1.00412575 0.00177775 0.21D-03 0.92D-04 13.23 3 1 1 1.25037546 -1.03902542 -295.63005184 -0.00045634 -0.00053825 0.22D-05 0.21D-06 22.16 4 1 1 1.25042940 -1.03905105 -295.63007747 -0.00002564 0.00001075 0.33D-07 0.24D-08 31.14 5 1 1 1.25043125 -1.03905184 -295.63007826 -0.00000079 -0.00000368 0.85D-09 0.19D-10 39.86 6 1 1 1.25043145 -1.03905192 -295.63007834 -0.00000008 0.00000013 0.26D-10 0.31D-12 48.59 Energies without level shift correction: 6 1 1 1.25043145 -0.93887934 -295.52990576 Energy contributions for state 1.4: =================================== Energy contr. SQ.Norm of FOWF Space I -0.00497660 0.00299455 Space S -0.20250553 0.08485163 Space P -0.73139721 0.16258527 ===================================== Analysis of CPU times by interactions ===================================== I S P I 4.1% S 16.5% 14.5% P 0.3% 58.7% 0.5% Initialization: 2.8% Other: 2.7% Total CPU: 48.6 seconds ===================================== gnormi= 1.00299455 gnorms= 0.08485163 gnormp= 0.16258527 gnorm= 1.25043145 ecorri= -0.00497660 ecorrs= -0.20250553 ecorrp= -0.73139721 ecorr= -1.03905192 Reference coefficients greater than 0.0500000 ============================================= 222220222222/2022\ 0.8256212 22222/222\222202/\ -0.2403899 222/20222\22220222 -0.2101464 2222202222222/02\2 -0.1893932 22222/222/222202\\ 0.1421301 22222022222222/2\0 0.1191487 22222022/\2222/22\ -0.1144520 22222/22\222220220 -0.1102548 222222222222/0022\ -0.0991184 2222//222222\2022\ 0.0984868 22222/222\222//2\\ 0.0879723 222220222222/\/22\ 0.0769436 22222022//2222\22\ 0.0747002 2222222222222/02\0 -0.0712018 222/2\2222222/022\ -0.0666579 2222//222222/\\22\ 0.0613390 2222/\222222//\22\ 0.0604122 2222/0222\22/2\222 -0.0572697 222/\022222222/22\ -0.0544065 22222/222\22/2\220 0.0535747 2222/\222222/2022\ 0.0517212 22222/222\22/\0222 -0.0509367 222220222222//\22\ 0.0505887 RESULTS FOR STATE 1.4 ===================== Coefficient of reference function: C(0) = 1.00000000 (fixed) 1.00000000 (relaxed) Energy contributions of configuration classes CLASS SQ.NORM ECORR1 ECORR2 +++++++++++++++++++++++++++++++++++++++++++++++++++ Internals 0.00299455 -0.00497660 1.02803672 Singles 0.08485163 -0.20250548 -0.44822316 Pairs 0.16258527 -0.73139720 -1.61886548 Total 1.25043145 -0.93887929 -1.03905192 +++++++++++++++++++++++++++++++++++++++++++++++++++ Reference energy -294.59102642 Nuclear energy 212.85767471 Kinetic energy 294.95163255 One electron energy -820.52087617 Two electron energy 312.03312313 Virial quotient -1.00230019 Correlation energy -1.03905192 !RSPT2 STATE 1.4 Energy -295.630078342397 Properties without orbital relaxation: !RSPT2 STATE 1.4 Dipole moment 0.00000000 0.00000000 0.00000000 Dipole moment /Debye 0.00000000 0.00000000 0.00000000 !RSPT expec <1.4|H|1.4> -295.409130357210 Correlation energy -1.02298288 !RSPT3 STATE 1.4 Energy -295.614009302467 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 968.81 500 700 610 900 950 970 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 19.59 500 610 700 1000 520 2100 2140 1001 2141 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF PROGRAMS * TOTAL RS3 RS3 MULTI INT RESTART CPU TIMES * 1068.10 529.02 510.59 3.54 24.83 0.01 REAL TIME * 1083.55 SEC DISK USED * 3.19 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= 0.40 Convergence thresholds: THRVAR = 1.00D-08 THRDEN = 1.00D-06 Number of optimized states: 1 Roots: 2 Number of reference states: 1 Roots: 2 Reference symmetry: 4 Singlet Number of electrons: 42 Maximum number of shells: 6 Maximum number of spin couplings: 42 Reference space: 350 conf 610 CSFs N elec internal: 36606 conf 88770 CSFs N-1 el internal: 75260 conf 358244 CSFs N-2 el internal: 40780 conf 348877 CSFs Number of electrons in valence space: 30 Maximum number of open shell orbitals in reference space: 6 Maximum number of open shell orbitals in internal spaces: 10 Number of core orbitals: 6 ( 2 0 1 0 2 0 1 0 ) Number of closed-shell orbitals: 8 ( 3 0 2 0 2 0 1 0 ) Number of active orbitals: 10 ( 1 2 1 1 1 2 1 1 ) Number of external orbitals: 298 ( 54 30 42 22 55 30 43 22 ) 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: 13 Reference wavefunction optimized for reference space (refopt=1) State Reference Energy 2 -294.52487275 1 -294.59102642 Number of blocks in overlap matrix: 16 Smallest eigenvalue: 0.35D-01 Number of N-2 electron functions: 324 Number of N-1 electron functions: 358244 Number of internal configurations: 11048 Number of singly external configurations: 13303514 Number of doubly external configurations: 1820790 Total number of contracted configurations: 15135352 Total number of uncontracted configurations: 2002837111 Weight factors for SA-density in H0: 1.000000 FIMAX= 0.11D+00 FXMAX= 0.71D-02 DIAG= F F NOREF=1 NOINT=0 IHPPD=2 Nuclear energy: 212.85767471 Core energy: -348.34609890 Zeroth-order valence energy: -21.94422947 Zeroth-order total energy: -157.43265366 First-order energy: -137.09221909 Diagonal Coupling coefficients finished. Storage:15286285 words, CPU-Time: 0.78 seconds. Energy denominators for pairs finished in 0 passes. Storage: 990576 words, CPU-time: 0.00 seconds. A level shift of 0.40 is applied. ITER. STATE ROOT SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) TIME 1 1 2 1.09441827 -0.03776731 -294.56264006 -0.03776731 -0.94556416 0.94D-01 0.17D+00 10.52 2 1 2 1.26063366 -1.04947645 -295.57434920 -1.01170914 0.00173694 0.25D-03 0.92D-04 19.35 3 1 2 1.25998155 -1.04991664 -295.57478939 -0.00044019 -0.00053511 0.40D-05 0.37D-06 28.21 4 1 2 1.26006084 -1.04995293 -295.57482568 -0.00003629 0.00001109 0.36D-07 0.75D-08 37.01 5 1 2 1.26006521 -1.04995473 -295.57482748 -0.00000180 -0.00000373 0.24D-08 0.71D-10 45.81 6 1 2 1.26006573 -1.04995494 -295.57482769 -0.00000021 0.00000013 0.25D-10 0.45D-11 54.59 7 1 2 1.26006587 -1.04995500 -295.57482775 -0.00000006 -0.00000005 0.26D-11 0.39D-13 63.37 Energies without level shift correction: 7 1 2 1.26006587 -0.94592865 -295.47080140 Energy contributions for state 1.4: =================================== Energy contr. SQ.Norm of FOWF Space I -0.00431151 0.00290860 Space S -0.20843039 0.09324043 Space P -0.73318674 0.16391685 ===================================== Analysis of CPU times by interactions ===================================== I S P I 13.1% S 14.8% 13.4% P 0.2% 53.7% 0.4% Initialization: 2.0% Other: 2.4% Total CPU: 63.4 seconds ===================================== gnormi= 1.00290860 gnorms= 0.09324043 gnormp= 0.16391685 gnorm= 1.26006587 ecorri= -0.00431151 ecorrs= -0.20843039 ecorrp= -0.73318674 ecorr= -1.04995500 Reference coefficients greater than 0.0500000 ============================================= 2222202222222/02\2 0.6386325 22222022222222/2\0 0.4849482 22222/222/222202\\ -0.2777316 2222222222222/02\0 -0.1700758 2222/022\222220222 -0.1659474 22222/22\222220220 0.1289182 2222//2222222\02\2 0.1257982 22222/222\22/\0222 -0.1142924 2222/\2222222/02\2 0.1048199 22222022222220/2\2 -0.1021303 22222/222\22/2\220 -0.0996179 22222/222\222202/\ -0.0937063 222220222222/\/22\ 0.0918263 22222/222/222/\2\\ -0.0904055 22222022/\2222/22\ -0.0851054 22222022//2222\22\ -0.0789502 222220222222/2022\ 0.0754973 2222202222222/22\0 -0.0730800 222220222222//\22\ -0.0728102 22222/222\222/\2/\ -0.0688408 2222//222222\2022\ -0.0664018 222/\022222222/22\ -0.0654963 222222222222/0022\ -0.0644914 22222/22\022220222 0.0632843 222/20222\22220222 -0.0588359 222/2/2222222\022\ 0.0557720 222/22222\22220220 0.0530760 22222/222/22\2\220 -0.0524759 RESULTS FOR STATE 2.4 ===================== Coefficient of reference function: C(0) = 1.00000000 (fixed) 1.00000000 (relaxed) Energy contributions of configuration classes CLASS SQ.NORM ECORR1 ECORR2 +++++++++++++++++++++++++++++++++++++++++++++++++++ Internals 0.00290860 -0.00431151 1.04038368 Singles 0.09324043 -0.20843039 -0.46270410 Pairs 0.16391685 -0.73318674 -1.62763457 Total 1.26006587 -0.94592864 -1.04995500 +++++++++++++++++++++++++++++++++++++++++++++++++++ Reference energy -294.52487275 Nuclear energy 212.85767471 Kinetic energy 295.31675192 One electron energy -820.50360176 Two electron energy 312.07109931 Virial quotient -1.00087389 Correlation energy -1.04995500 !RSPT2 STATE 2.4 Energy -295.574827746023 Properties without orbital relaxation: !RSPT2 STATE 2.4 Dipole moment 0.00000000 0.00000000 0.00000000 Dipole moment /Debye 0.00000000 0.00000000 0.00000000 !RSPT expec <2.4|H|2.4> -295.338795047078 Correlation energy -1.02559572 !RSPT3 STATE 2.4 Energy -295.550468467603 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 968.81 500 700 610 900 950 970 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 19.59 500 610 700 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 * 1629.07 560.97 529.02 510.59 3.54 24.83 0.01 REAL TIME * 1650.84 SEC DISK USED * 3.19 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= 0.40 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: 42 Maximum number of shells: 6 Maximum number of spin couplings: 42 Reference space: 390 conf 670 CSFs N elec internal: 36606 conf 88770 CSFs N-1 el internal: 76788 conf 358740 CSFs N-2 el internal: 44177 conf 350834 CSFs Number of electrons in valence space: 30 Maximum number of open shell orbitals in reference space: 6 Maximum number of open shell orbitals in internal spaces: 10 Number of core orbitals: 6 ( 2 0 1 0 2 0 1 0 ) Number of closed-shell orbitals: 8 ( 3 0 2 0 2 0 1 0 ) Number of active orbitals: 10 ( 1 2 1 1 1 2 1 1 ) Number of external orbitals: 298 ( 54 30 42 22 55 30 43 22 ) 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: 2 Reference wavefunction optimized for reference space (refopt=1) State Reference Energy 1 -294.78883369 Number of blocks in overlap matrix: 16 Smallest eigenvalue: 0.57D-02 Number of N-2 electron functions: 324 Number of N-1 electron functions: 358740 Number of internal configurations: 11301 Number of singly external configurations: 13307036 Number of doubly external configurations: 1820790 Total number of contracted configurations: 15139127 Total number of uncontracted configurations: 2014158243 Weight factors for SA-density in H0: 1.000000 FIMAX= 0.11D+00 FXMAX= 0.92D-02 DIAG= F F NOREF=1 NOINT=0 IHPPD=2 Nuclear energy: 212.85767471 Core energy: -348.34609890 Zeroth-order valence energy: -15.98903943 Zeroth-order total energy: -151.47746362 First-order energy: -143.31137007 Diagonal Coupling coefficients finished. Storage:15543204 words, CPU-Time: 0.80 seconds. Energy denominators for pairs finished in 0 passes. Storage: 1001177 words, CPU-time: 0.00 seconds. A level shift of 0.40 is applied. ITER. STATE ROOT SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) TIME 1 1 1 1.06422000 -0.02568800 -294.81452169 -0.02568800 -0.90095646 0.64D-01 0.16D+00 4.00 2 1 1 1.22356392 -0.99352756 -295.78236125 -0.96783956 0.00044829 0.84D-04 0.91D-04 13.04 3 1 1 1.22386502 -0.99415969 -295.78299338 -0.00063213 -0.00043322 0.81D-06 0.13D-06 22.09 4 1 1 1.22389785 -0.99417505 -295.78300874 -0.00001536 0.00000022 0.48D-08 0.17D-08 31.13 5 1 1 1.22389785 -0.99417507 -295.78300876 -0.00000002 -0.00000201 0.54D-10 0.94D-11 40.15 Energies without level shift correction: 5 1 1 1.22389785 -0.90461593 -295.69344962 Energy contributions for state 1.1: =================================== Energy contr. SQ.Norm of FOWF Space I -0.00402945 0.00168119 Space S -0.17795851 0.06413822 Space P -0.72262797 0.15807844 ===================================== Analysis of CPU times by interactions ===================================== I S P I 4.4% S 16.7% 14.4% P 0.3% 57.8% 0.5% Initialization: 3.2% Other: 2.6% Total CPU: 40.1 seconds ===================================== gnormi= 1.00168119 gnorms= 0.06413822 gnormp= 0.15807844 gnorm= 1.22389785 ecorri= -0.00402945 ecorrs= -0.17795851 ecorrp= -0.72262797 ecorr= -0.99417507 Reference coefficients greater than 0.0500000 ============================================= 222220222222220220 0.9220333 22222/222\222/022\ 0.1931103 222220222022220222 -0.1769058 222222222222200220 -0.1329024 2222/0222\2222/22\ 0.1305380 2222/\2222222/\220 0.0844002 2222//2222222\\220 0.0824328 222220222222200222 -0.0572967 22222/222/222\022\ -0.0557234 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 0.00168119 -0.00402945 0.98531831 Singles 0.06413822 -0.17795851 -0.39115366 Pairs 0.15807844 -0.72262796 -1.58833972 Total 1.22389785 -0.90461592 -0.99417507 +++++++++++++++++++++++++++++++++++++++++++++++++++ Reference energy -294.78883369 Nuclear energy 212.85767471 Kinetic energy 294.94217115 One electron energy -820.46872611 Two electron energy 311.82804265 Virial quotient -1.00285086 Correlation energy -0.99417507 !RSPT2 STATE 1.1 Energy -295.783008757298 Properties without orbital relaxation: !RSPT2 STATE 1.1 Dipole moment 0.00000000 0.00000000 0.00000000 Dipole moment /Debye 0.00000000 0.00000000 0.00000000 !RSPT expec <1.1|H|1.1> -295.612726605535 Correlation energy -1.00836085 !RSPT3 STATE 1.1 Energy -295.797194538456 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 968.81 500 700 610 900 950 970 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 19.59 500 610 700 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 * 2170.40 541.33 560.97 529.02 510.59 3.54 24.83 0.01 REAL TIME * 2197.08 SEC DISK USED * 3.19 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= 0.40 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: 4 Singlet Number of electrons: 42 Maximum number of shells: 6 Maximum number of spin couplings: 42 Reference space: 350 conf 610 CSFs N elec internal: 36606 conf 88770 CSFs N-1 el internal: 75260 conf 358244 CSFs N-2 el internal: 40780 conf 348877 CSFs Number of electrons in valence space: 30 Maximum number of open shell orbitals in reference space: 6 Maximum number of open shell orbitals in internal spaces: 10 Number of core orbitals: 6 ( 2 0 1 0 2 0 1 0 ) Number of closed-shell orbitals: 8 ( 3 0 2 0 2 0 1 0 ) Number of active orbitals: 10 ( 1 2 1 1 1 2 1 1 ) Number of external orbitals: 298 ( 54 30 42 22 55 30 43 22 ) 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: 13 Reference wavefunction optimized for reference space (refopt=1) State Reference Energy 1 -294.59102642 Number of blocks in overlap matrix: 16 Smallest eigenvalue: 0.37D-01 Number of N-2 electron functions: 324 Number of N-1 electron functions: 358244 Number of internal configurations: 11048 Number of singly external configurations: 13303514 Number of doubly external configurations: 1820790 Total number of contracted configurations: 15135352 Total number of uncontracted configurations: 2002837111 Weight factors for SA-density in H0: 1.000000 FIMAX= 0.11D+00 FXMAX= 0.35D-02 DIAG= F F NOREF=1 NOINT=0 IHPPD=2 Nuclear energy: 212.85767471 Core energy: -348.34609890 Zeroth-order valence energy: -15.24707137 Zeroth-order total energy: -150.73549557 First-order energy: -143.85553085 Diagonal Coupling coefficients finished. Storage:15286285 words, CPU-Time: 0.68 seconds. Energy denominators for pairs finished in 0 passes. Storage: 990576 words, CPU-time: 0.00 seconds. A level shift of 0.40 is applied. ITER. STATE ROOT SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) TIME 1 1 1 1.07242438 -0.02896975 -294.61999617 -0.02896975 -0.91877092 0.72D-01 0.16D+00 3.84 2 1 1 1.23369054 -1.01290562 -295.60393204 -0.98393587 0.00156104 0.13D-03 0.77D-04 12.78 3 1 1 1.23309720 -1.01320877 -295.60423519 -0.00030315 -0.00043522 0.11D-05 0.15D-06 21.70 4 1 1 1.23314478 -1.01323041 -295.60425683 -0.00002164 0.00000730 0.10D-07 0.15D-08 30.57 5 1 1 1.23314509 -1.01323055 -295.60425697 -0.00000014 -0.00000229 0.16D-09 0.95D-11 39.43 6 1 1 1.23314527 -1.01323062 -295.60425704 -0.00000007 0.00000006 0.31D-11 0.11D-12 48.50 Energies without level shift correction: 6 1 1 1.23314527 -0.91997251 -295.51099893 Energy contributions for state 1.4: =================================== Energy contr. SQ.Norm of FOWF Space I -0.00437847 0.00217351 Space S -0.18954544 0.07142943 Space P -0.72604861 0.15954233 ===================================== Analysis of CPU times by interactions ===================================== I S P I 3.6% S 16.5% 14.7% P 0.3% 59.5% 0.5% Initialization: 2.4% Other: 2.7% Total CPU: 48.5 seconds ===================================== gnormi= 1.00217351 gnorms= 0.07142943 gnormp= 0.15954233 gnorm= 1.23314527 ecorri= -0.00437847 ecorrs= -0.18954544 ecorrp= -0.72604861 ecorr= -1.01323062 Reference coefficients greater than 0.0500000 ============================================= 222220222222/2022\ 0.8256212 22222/222\222202/\ -0.2403899 222/20222\22220222 -0.2101464 2222202222222/02\2 -0.1893932 22222/222/222202\\ 0.1421301 22222022222222/2\0 0.1191487 22222022/\2222/22\ -0.1144520 22222/22\222220220 -0.1102548 222222222222/0022\ -0.0991184 2222//222222\2022\ 0.0984868 22222/222\222//2\\ 0.0879723 222220222222/\/22\ 0.0769436 22222022//2222\22\ 0.0747002 2222222222222/02\0 -0.0712018 222/2\2222222/022\ -0.0666579 2222//222222/\\22\ 0.0613390 2222/\222222//\22\ 0.0604122 2222/0222\22/2\222 -0.0572697 222/\022222222/22\ -0.0544065 22222/222\22/2\220 0.0535747 2222/\222222/2022\ 0.0517212 22222/222\22/\0222 -0.0509367 222220222222//\22\ 0.0505887 RESULTS FOR STATE 1.4 ===================== Coefficient of reference function: C(0) = 1.00000000 (fixed) 1.00000000 (relaxed) Energy contributions of configuration classes CLASS SQ.NORM ECORR1 ECORR2 +++++++++++++++++++++++++++++++++++++++++++++++++++ Internals 0.00217351 -0.00437847 1.00358596 Singles 0.07142943 -0.18954542 -0.41751950 Pairs 0.15954233 -0.72604860 -1.59929708 Total 1.23314527 -0.91997248 -1.01323062 +++++++++++++++++++++++++++++++++++++++++++++++++++ Reference energy -294.59102642 Nuclear energy 212.85767471 Kinetic energy 294.95260119 One electron energy -820.55924442 Two electron energy 312.09731268 Virial quotient -1.00220936 Correlation energy -1.01323062 !RSPT2 STATE 1.4 Energy -295.604257037878 Properties without orbital relaxation: !RSPT2 STATE 1.4 Dipole moment 0.00000000 0.00000000 0.00000000 Dipole moment /Debye 0.00000000 0.00000000 0.00000000 !RSPT expec <1.4|H|1.4> -295.419070094702 Correlation energy -1.02109813 !RSPT3 STATE 1.4 Energy -295.612124554465 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 968.81 500 700 610 900 950 970 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 19.59 500 610 700 1000 520 2100 2140 1001 2141 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF PROGRAMS * TOTAL RS3 RS3 RS3 RS3 RS3 MULTI INT RESTART CPU TIMES * 2695.08 524.68 541.33 560.97 529.02 510.59 3.54 24.83 0.01 REAL TIME * 2727.19 SEC DISK USED * 3.19 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= 0.40 Convergence thresholds: THRVAR = 1.00D-08 THRDEN = 1.00D-06 Number of optimized states: 1 Roots: 2 Number of reference states: 1 Roots: 2 Reference symmetry: 4 Singlet Number of electrons: 42 Maximum number of shells: 6 Maximum number of spin couplings: 42 Reference space: 350 conf 610 CSFs N elec internal: 36606 conf 88770 CSFs N-1 el internal: 75260 conf 358244 CSFs N-2 el internal: 40780 conf 348877 CSFs Number of electrons in valence space: 30 Maximum number of open shell orbitals in reference space: 6 Maximum number of open shell orbitals in internal spaces: 10 Number of core orbitals: 6 ( 2 0 1 0 2 0 1 0 ) Number of closed-shell orbitals: 8 ( 3 0 2 0 2 0 1 0 ) Number of active orbitals: 10 ( 1 2 1 1 1 2 1 1 ) Number of external orbitals: 298 ( 54 30 42 22 55 30 43 22 ) 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: 13 Reference wavefunction optimized for reference space (refopt=1) State Reference Energy 2 -294.52487275 1 -294.59102642 Number of blocks in overlap matrix: 16 Smallest eigenvalue: 0.35D-01 Number of N-2 electron functions: 324 Number of N-1 electron functions: 358244 Number of internal configurations: 11048 Number of singly external configurations: 13303514 Number of doubly external configurations: 1820790 Total number of contracted configurations: 15135352 Total number of uncontracted configurations: 2002837111 Weight factors for SA-density in H0: 1.000000 FIMAX= 0.11D+00 FXMAX= 0.71D-02 DIAG= F F NOREF=1 NOINT=0 IHPPD=2 Nuclear energy: 212.85767471 Core energy: -348.34609890 Zeroth-order valence energy: -15.03809027 Zeroth-order total energy: -150.52651447 First-order energy: -143.99835828 Diagonal Coupling coefficients finished. Storage:15286285 words, CPU-Time: 0.68 seconds. Energy denominators for pairs finished in 0 passes. Storage: 990576 words, CPU-time: 0.00 seconds. A level shift of 0.40 is applied. ITER. STATE ROOT SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) TIME 1 1 2 1.07480807 -0.02992323 -294.55479598 -0.02992323 -0.92178175 0.75D-01 0.16D+00 9.37 2 1 2 1.23635504 -1.01585059 -295.54072334 -0.98592736 0.00151262 0.15D-03 0.66D-04 18.28 3 1 2 1.23549681 -1.01604250 -295.54091525 -0.00019191 -0.00040419 0.10D-05 0.21D-06 27.19 4 1 2 1.23556224 -1.01607126 -295.54094401 -0.00002876 0.00000721 0.96D-08 0.16D-08 36.29 5 1 2 1.23556201 -1.01607118 -295.54094393 0.00000008 -0.00000205 0.12D-09 0.17D-10 45.21 Energies without level shift correction: 5 1 2 1.23556201 -0.92184638 -295.44671913 Energy contributions for state 1.4: =================================== Energy contr. SQ.Norm of FOWF Space I -0.00367259 0.00186572 Space S -0.19197202 0.07386520 Space P -0.72620176 0.15983108 ===================================== Analysis of CPU times by interactions ===================================== I S P I 16.1% S 14.2% 12.5% P 0.3% 51.6% 0.4% Initialization: 2.5% Other: 2.3% Total CPU: 45.2 seconds ===================================== gnormi= 1.00186572 gnorms= 0.07386520 gnormp= 0.15983108 gnorm= 1.23556201 ecorri= -0.00367259 ecorrs= -0.19197202 ecorrp= -0.72620176 ecorr= -1.01607118 Reference coefficients greater than 0.0500000 ============================================= 2222202222222/02\2 0.6386325 22222022222222/2\0 0.4849482 22222/222/222202\\ -0.2777316 2222222222222/02\0 -0.1700758 2222/022\222220222 -0.1659474 22222/22\222220220 0.1289182 2222//2222222\02\2 0.1257982 22222/222\22/\0222 -0.1142924 2222/\2222222/02\2 0.1048199 22222022222220/2\2 -0.1021303 22222/222\22/2\220 -0.0996179 22222/222\222202/\ -0.0937063 222220222222/\/22\ 0.0918263 22222/222/222/\2\\ -0.0904055 22222022/\2222/22\ -0.0851054 22222022//2222\22\ -0.0789502 222220222222/2022\ 0.0754973 2222202222222/22\0 -0.0730800 222220222222//\22\ -0.0728102 22222/222\222/\2/\ -0.0688408 2222//222222\2022\ -0.0664018 222/\022222222/22\ -0.0654963 222222222222/0022\ -0.0644914 22222/22\022220222 0.0632843 222/20222\22220222 -0.0588359 222/2/2222222\022\ 0.0557720 222/22222\22220220 0.0530760 22222/222/22\2\220 -0.0524759 RESULTS FOR STATE 2.4 ===================== Coefficient of reference function: C(0) = 1.00000000 (fixed) 1.00000000 (relaxed) Energy contributions of configuration classes CLASS SQ.NORM ECORR1 ECORR2 +++++++++++++++++++++++++++++++++++++++++++++++++++ Internals 0.00186572 -0.00367259 1.00797528 Singles 0.07386520 -0.19197207 -0.42318821 Pairs 0.15983108 -0.72620178 -1.60085825 Total 1.23556201 -0.92184643 -1.01607118 +++++++++++++++++++++++++++++++++++++++++++++++++++ Reference energy -294.52487275 Nuclear energy 212.85767471 Kinetic energy 295.33129925 One electron energy -820.58210248 Two electron energy 312.18348384 Virial quotient -1.00070986 Correlation energy -1.01607118 !RSPT2 STATE 2.4 Energy -295.540943929507 Properties without orbital relaxation: !RSPT2 STATE 2.4 Dipole moment 0.00000000 0.00000000 0.00000000 Dipole moment /Debye 0.00000000 0.00000000 0.00000000 !RSPT expec <2.4|H|2.4> -295.352543190966 Correlation energy -1.02263848 !RSPT3 STATE 2.4 Energy -295.547511225096 ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 968.81 500 700 610 900 950 970 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 19.59 500 610 700 1000 520 2100 2140 1001 2141 VAR BASINP GEOM BASIS MCVARS RHF MCSCF BASIS MCSCF PROGRAMS * TOTAL RS3 RS3 RS3 RS3 RS3 RS3 MULTI INT RESTART CPU TIMES * 3215.95 520.87 524.68 541.33 560.97 529.02 510.59 3.54 24.83 0.01 REAL TIME * 3252.85 SEC DISK USED * 3.19 GB ********************************************************************************************************************************** RS3/aug-cc-pVTZ energy= -295.547511225096 RS3 RS3 RS3 RS3 RS3 RS3 MULTI -295.54751123 -295.61212455 -295.79719454 -295.55046847 -295.61400930 -295.79724101 -294.52487275 ********************************************************************************************************************************** Molpro calculation terminated