Running default procedure: HF-SCF000 UCCSD(T)-F12 Generated 15 symmetrical displacements Number of displacements for numerical gradient: 30 Starting numerical gradient for UCCSD(T)-F12 Starting task 1 Incrementing displacement 1 by 1. CPU= 0.00 sec, Elapsed= 0.00 sec Recomputing integrals since geometry changed PROGRAM * SEWARD (Integral evaluation for generally contracted gaussian basis sets) Author: Roland Lindh, 1990 Geometry written to block 1 of record 700 Point group C1 ATOMIC COORDINATES NR ATOM CHARGE X Y Z 1 C 6.00 2.779366499 1.179484970 -0.183977959 2 C 6.00 2.780092489 -1.179256060 -0.179166912 3 H 1.00 3.678520083 2.972522646 -0.376066489 4 H 1.00 3.675970845 -2.972423471 -0.385071748 5 O 8.00 -0.514835212 -2.199888171 0.631443628 6 S 16.00 -2.007711171 -0.001827818 -0.438325757 7 O 8.00 -0.516159680 2.201401131 0.622614535 Bond lengths in Bohr (Angstrom) 1-2 2.358746048 1-3 2.015033319 1-7 3.543359548 2-4 2.015054390 2-5 3.543349814 ( 1.248194655) ( 1.066309712) ( 1.875065123) ( 1.066320862) ( 1.875059972) 5-6 2.864359349 6-7 2.864356464 ( 1.515753691) ( 1.515752165) Bond angles 1-2-4 152.84961883 1-2-5 106.75150262 1-7-6 100.26237469 2-1-3 152.85886093 2-1-7 106.75169085 2-5-6 100.26328656 3-1-7 100.37456814 4-2-5 100.39742528 5-6-7 100.40063706 NUCLEAR CHARGE: 46 NUMBER OF PRIMITIVE AOS: 256 NUMBER OF SYMMETRY AOS: 245 NUMBER OF CONTRACTIONS: 177 ( 177A ) NUMBER OF INNER CORE ORBITALS: 1 ( 1A ) NUMBER OF OUTER CORE ORBITALS: 8 ( 8A ) NUMBER OF VALENCE ORBITALS: 22 ( 22A ) NUCLEAR REPULSION ENERGY 225.16524921 Basis set: DF Basis size: 426 Attributes: Sphericals: T Basis set: JK Basis size: 536 Attributes: Sphericals: T Basis set: RI Basis size: 374 Attributes: Sphericals: T Eigenvalues of metric 1 0.146E-03 0.261E-03 0.100E-02 0.116E-02 0.123E-02 0.133E-02 0.142E-02 0.185E-02 Contracted 2-electron integrals neglected if value below 1.0D-11 AO integral compression algorithm 1 Integral accuracy 1.0D-11 583.008 MB (compressed) written to integral file ( 48.1%) NUMBER OF SORTED TWO-ELECTRON INTEGRALS: 124086381. BUFFER LENGTH: 32768 NUMBER OF SEGMENTS: 8 SEGMENT LENGTH: 15999503 RECORD LENGTH: 524288 Memory used in sort: 16.56 MW SORT1 READ 151607981. AND WROTE 119883982. INTEGRALS IN 348 RECORDS. CPU TIME: 1.23 SEC, REAL TIME: 1.87 SEC SORT2 READ 119883982. AND WROTE 124086381. INTEGRALS IN 2224 RECORDS. CPU TIME: 1.45 SEC, REAL TIME: 1.89 SEC FILE SIZES: FILE 1: 614.3 MBYTE, FILE 4: 1459.7 MBYTE, TOTAL: 2073.9 MBYTE OPERATOR DM FOR CENTER 0 COORDINATES: 0.000000 0.000000 0.000000 PROGRAM * RHF-SCF (CLOSED SHELL) Authors: W. Meyer, H.-J. Werner NUMBER OF ELECTRONS: 23+ 23- SPACE SYMMETRY=1 SPIN SYMMETRY: Singlet CONVERGENCE THRESHOLDS: 1.00E-07 (Density) 1.00E-08 (Energy) MAX. NUMBER OF ITERATIONS: 60 INTERPOLATION TYPE: DIIS INTERPOLATION STEPS: 2 (START) 1 (STEP) LEVEL SHIFTS: 0.00 (CLOSED) 0.00 (OPEN) Number of closed-shell orbitals: 23 ( 23 ) Molecular orbitals read from record 2100.2 Type=RHF/CANONICAL (state 1.1) Molecular orbital dump at record 2100.1 ITERATION DDIFF GRAD ENERGY 2-EL.EN. DIPOLE MOMENTS DIIS ORB. 1 0.000D+00 0.000D+00 -624.00826010 915.616799 0.95274 -0.00226 -0.44550 0 start 2 0.000D+00 0.398D-04 -624.00826682 915.616725 0.95276 -0.00057 -0.44549 1 diag 3 0.943D-04 0.959D-05 -624.00826753 915.616772 0.95274 -0.00148 -0.44550 2 diag 4 0.204D-04 0.350D-05 -624.00826759 915.616742 0.95276 -0.00036 -0.44550 3 diag 5 0.604D-05 0.226D-05 -624.00826762 915.616750 0.95276 -0.00080 -0.44550 4 diag 6 0.338D-05 0.624D-06 -624.00826763 915.616758 0.95276 -0.00078 -0.44550 5 diag 7 0.191D-05 0.288D-06 -624.00826763 915.616751 0.95277 -0.00076 -0.44549 6 diag 8 0.106D-05 0.130D-06 -624.00826763 915.616757 0.95276 -0.00077 -0.44550 7 orth 9 0.372D-06 0.502D-07 -624.00826763 915.616755 0.95277 -0.00077 -0.44550 8 diag 10 0.175D-06 0.201D-07 -624.00826763 915.616757 0.95277 -0.00077 -0.44550 9 diag 11 0.668D-07 0.688D-08 -624.00826763 915.616756 0.95277 -0.00077 -0.44550 0 orth Final occupancy: 23 !RHF STATE 1.1 Energy -624.008267633437 Nuclear energy 225.16524921 One-electron energy -1306.98189470 Two-electron energy 457.80837786 Virial quotient -1.00049562 !RHF STATE 1.1 Dipole moment 0.95276600 -0.00076975 -0.44549535 Dipole moment /Debye 2.42153100 -0.00195637 -1.13226208 Orbital energies: 1.1 2.1 3.1 4.1 5.1 6.1 7.1 8.1 9.1 10.1 -92.059880 -20.620288 -20.620211 -11.316462 -11.313615 -9.051443 -6.733410 -6.731973 -6.729749 -1.454218 11.1 12.1 13.1 14.1 15.1 16.1 17.1 18.1 19.1 20.1 -1.343246 -1.085406 -0.865168 -0.816175 -0.721491 -0.653298 -0.648761 -0.645480 -0.520381 -0.511950 21.1 22.1 23.1 24.1 25.1 -0.492325 -0.440031 -0.307608 0.024979 0.053950 HOMO 23.1 -0.307608 = -8.3704eV LUMO 24.1 0.024979 = 0.6797eV LUMO-HOMO 0.332587 = 9.0501eV ********************************************************************************************************************************** DATASETS * FILE NREC LENGTH (MB) RECORD NAMES 1 20 519.55 500 610 700 900 950 970 1000 129 960 1100 VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S 1400 1410 1200 1210 1080 1600 1650 1300 1700 2100 T V H0 H01 AOSYM SMH MOLCAS ERIS OPER RHF 2 6 4.14 700 1000 520 2100 7360 5600 GEOM BASIS MCVARS RHF F12ABS GINFO PROGRAMS * TOTAL HF-SCF UCCSD(T) HF-SCF INT CPU TIMES * 1079.45 13.80 1048.11 9.98 7.22 REAL TIME * 1121.85 SEC DISK USED * 6.70 GB ********************************************************************************************************************************** Basis set: DF Basis size: 426 Attributes: Sphericals: T Basis set: JK Basis size: 536 Attributes: Sphericals: T Basis set: RI Basis size: 374 Attributes: Sphericals: T PROGRAM * CCSD (Unrestricted open-shell coupled cluster) Authors: C. Hampel, H.-J. Werner, 1991, M. Deegan, P.J. Knowles, 1992 UCCSD-F12 implementation by G. Knizia and H.-J. Werner, 2008 Density fitting integral evaluation by F.R. Manby, 2003,2007, G. Knizia, 2010 Convergence thresholds: THRVAR = 1.00D-12 THRDEN = 1.00D-08 CCSD(T) terms to be evaluated (factor= 1.000) Number of core orbitals: 9 ( 9 ) Number of closed-shell orbitals: 14 ( 14 ) Number of external orbitals: 154 ( 154 ) Number of N-1 electron functions: 28 Number of N-2 electron functions: 378 Number of singly external CSFs: 4312 Number of doubly external CSFs: 6792478 Total number of CSFs: 6796790 Molecular orbitals read from record 2100.1 Type=RHF/CANONICAL (state 1.1) Integral transformation finished. Total CPU: 4.37 sec, npass= 1 Memory used: 47.93 MW Geminal basis: OPTFULL GEM_TYPE=SLATER BETA=1.0 NGEM=6 Optimizing Gaussian exponents for each gem_beta Geminal optimization for beta= 1.0000 Weight function: m=0, omega= 1.4646 Augmented Hessian optimization of geminal fit. Trust ratio= 0.40000 Convergence reached after 2 iterations. Final gradient= 8.66D-16, Step= 4.23D-06, Delta= 1.28D-09 Alpha: 0.19532 0.81920 2.85917 9.50073 35.69989 197.79328 Coeff: 0.27070 0.30552 0.18297 0.10986 0.06810 0.04224 WFN_F12=FIX,EG DECOUPLE_EXPL=F HYBRID=0 NOX=F SEMIINT_F12=T CORE_SINGLES=F AO(A)-basis ORBITAL loaded. Number of functions: 177 RI(R)-basis RI loaded. Number of functions: 374 DF-basis JK loaded. Number of functions: 536 Screening thresholds: THRAO= 1.00D-11 THRMO= 1.00D-11 THRPROD= 1.00D-11 THRSW= 1.00D-08 THROV= 1.00D-12 THRAOF12= 1.00D-08 CPU time for one-electron matrices 3.09 sec Reading frozen CA basis information from record 7360.2. Construction of ABS: Pseudo-inverse stability 1.12E-11 Smallest eigenvalue of S 6.37E-05 (threshold= 1.00E-08) Ratio eigmin/eigmax 9.12E-06 (threshold= 1.00E-09) Smallest eigenvalue of S kept 6.37E-05 (threshold= 6.37E-05, 0 functions deleted, 374 kept) Construction of CABS: Pseudo-inverse stability 6.60E-11 Smallest eigenvalue of S 5.66E-06 (threshold= 1.00E-08) Ratio eigmin/eigmax 5.66E-06 (threshold= 1.00E-09) Smallest eigenvalue of S kept 5.66E-06 (threshold= 5.66E-06, 0 functions deleted, 374 kept) CPU time for basis constructions 0.04 sec Fock operators(MO) rebuilt from dump record. CPU time for fock operators 0.04 sec TOTAL ALPHA BETA Singles Contributions MO -0.000000000 -0.000000000 -0.000000000 Singles Contributions CABS -0.021558145 -0.010779072 -0.010779072 Pure DF-RHF relaxation -0.021558145 CPU time for singles 0.13 sec AO(A)-basis ORBITAL loaded. Number of functions: 177 RI(R)-basis RI loaded. Number of functions: 374 DF-basis DF loaded. Number of functions: 426 Screening thresholds: THRAO= 1.00D-11 THRMO= 1.00D-11 THRPROD= 1.00D-11 THRSW= 1.00D-08 THROV= 1.00D-12 THRAOF12= 1.00D-08 CPU time for transformed integrals 11.01 sec CPU time for F12 matrices 1.60 sec Diagonal F12 ansatz with fixed amplitudes: TS= 0.5000 TT= 0.2500 TN= 0.3750 ITER. SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE VAR CPU MICRO DIIS 1 1.33994676 -1.13208735 -625.16191312 -1.1536E+00 3.40E-01 0.08 1 1 1 0 0 2 1.33994676 -1.13208735 -625.16191312 -2.1760E-14 7.82E-27 0.31 0 0 0 0 0 - - Continuing with F12/conv. amplitude coupling turned on. 3 1.34110476 -1.13652058 -625.16634636 -4.4332E-03 2.01E-04 0.60 1 1 1 1 1 4 1.34110476 -1.13652058 -625.16634636 0.0000E+00 4.04E-28 0.86 1 1 1 0 1 CPU time for iterative RMP2-F12 0.86 sec DF-RMP2-F12 doubles corrections: - - - - - - - - - - - - - - - - Approx. TOTAL A-B A-A B-B RMP2-F12/3C(FIX) -0.202579373 -0.176309168 -0.013135103 -0.013135103 RMP2-F12/3*C(FIX) -0.198146139 -0.173308585 -0.012418777 -0.012418777 RMP2-F12/3*C(DX) -0.199261501 -0.174119079 -0.012571211 -0.012571211 RMP2-F12/3*C(FIX,DX) -0.202019416 -0.179087593 -0.011465911 -0.011465911 DF-RMP2-F12 doubles energies: - - - - - - - - - - - - - - - Approx. TOTAL A-B A-A B-B RMP2 -0.933941206 -0.678203322 -0.127868942 -0.127868942 RMP2-F12/3C(FIX) -1.136520580 -0.854512490 -0.141004045 -0.141004045 RMP2-F12/3*C(FIX) -1.132087346 -0.851511907 -0.140287719 -0.140287719 RMP2-F12/3*C(DX) -1.133202708 -0.852322400 -0.140440154 -0.140440154 RMP2-F12/3*C(FIX,DX) -1.135960622 -0.857290915 -0.139334853 -0.139334853 Reference energy -624.008267633436 CABS relaxation correction to RHF -0.021558144765 New reference energy -624.029825778201 RMP2-F12 singles (MO) energy -0.000000000000 RMP2-F12 pair energy -1.136520579571 RMP2-F12 correlation energy -1.136520579572 !RMP2-F12/3C(FIX) energy -625.166346357773 Starting RMP2 calculation, locsing= 0 ITER. SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) DIIS TIME 1 1.33325705 -0.92841032 -624.93667795 -0.92841032 -0.00481692 0.88D-14 0.25D-02 1 1 22.34 2 1.33953022 -0.93366453 -624.94193217 -0.00525421 -0.00001454 0.23D-15 0.12D-04 2 2 22.72 3 1.33985989 -0.93380562 -624.94207326 -0.00014109 -0.00000009 0.42D-17 0.94D-07 3 3 23.13 4 1.33987319 -0.93380819 -624.94207582 -0.00000256 -0.00000000 0.53D-19 0.43D-09 4 4 23.57 5 1.33987353 -0.93380826 -624.94207589 -0.00000007 -0.00000000 0.94D-21 0.10D-11 5 5 24.04 6 1.33987353 -0.93380826 -624.94207589 -0.00000000 -0.00000000 0.31D-22 0.39D-14 6 6 24.53 Norm of t1 vector: 0.00000055 S-energy: -0.00000000 T1 diagnostic: 0.00000007 Norm of t2 vector: 0.58298673 P-energy: -0.93380826 Alpha-Beta: -0.67901013 Alpha-Alpha: -0.12739907 Beta-Beta: -0.12739907 Spin contamination 0.00000000 Reference energy -624.008267633436 CABS singles correction -0.021558144765 New reference energy -624.029825778201 RHF-RMP2 correlation energy -0.933808257871 !RHF-RMP2 energy -624.963634036072 F12/3C(FIX) correction -0.202579373360 RHF-RMP2-F12 correlation energy -1.136387631231 !RHF-RMP2-F12 total energy -625.166213409432 Starting UCCSD calculation ITER. SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) DIIS TIME 1 1.29570383 -0.86993483 -624.87820246 -0.86993483 -0.03350987 0.11D-01 0.66D-02 1 1 47.40 2 1.32549959 -0.89718911 -624.90545675 -0.02725429 -0.00384217 0.58D-03 0.15D-02 2 2 69.83 3 1.34404524 -0.90278926 -624.91105690 -0.00560015 -0.00075061 0.71D-03 0.15D-03 3 3 92.22 4 1.35573773 -0.90568507 -624.91395270 -0.00289581 -0.00026366 0.25D-03 0.55D-04 4 4 114.70 5 1.36730072 -0.90687783 -624.91514546 -0.00119276 -0.00011575 0.16D-03 0.14D-04 5 5 137.15 6 1.37736870 -0.90736402 -624.91563166 -0.00048619 -0.00004673 0.53D-04 0.82D-05 6 6 159.65 7 1.38805369 -0.90776884 -624.91603648 -0.00040482 -0.00001352 0.13D-04 0.28D-05 6 2 182.11 8 1.39344720 -0.90791324 -624.91618087 -0.00014440 -0.00000275 0.17D-05 0.77D-06 6 1 204.58