***************** * O R C A * ***************** --- An Ab Initio, DFT and Semiempirical electronic structure package --- ####################################################### # -***- # # Department of molecular theory and spectroscopy # # Directorship: Frank Neese # # Max Planck Institute for Chemical Energy Conversion # # D-45470 Muelheim/Ruhr # # Germany # # # # All rights reserved # # -***- # ####################################################### Program Version 3.0.3 - RELEASE - With contributions from (in alphabetic order): Ute Becker : Parallelization Dmytro Bykov : SCF Hessian Dmitry Ganyushin : Spin-Orbit,Spin-Spin,Magnetic field MRCI Andreas Hansen : Spin unrestricted coupled pair/coupled cluster methods Dimitrios Liakos : Extrapolation schemes; parallel MDCI Robert Izsak : Overlap fitted RIJCOSX, COSX-SCS-MP3 Christian Kollmar : KDIIS, OOCD, Brueckner-CCSD(T), CCSD density Simone Kossmann : Meta GGA functionals, TD-DFT gradient, OOMP2, MP2 Hessian Taras Petrenko : DFT Hessian,TD-DFT gradient, ASA and ECA modules, normal mode analysis, Resonance Raman, ABS, FL, XAS/XES, NRVS Christoph Reimann : Effective Core Potentials Michael Roemelt : Restricted open shell CIS Christoph Riplinger : Improved optimizer, TS searches, QM/MM, DLPNO-CCSD Barbara Sandhoefer : DKH picture change effects Igor Schapiro : Molecular dynamics Kantharuban Sivalingam : CASSCF convergence, NEVPT2 Boris Wezisla : Elementary symmetry handling Frank Wennmohs : Technical directorship We gratefully acknowledge several colleagues who have allowed us to interface, adapt or use parts of their codes: Stefan Grimme, W. Hujo, H. Kruse, T. Risthaus : VdW corrections, initial TS optimization, DFT functionals, gCP Ed Valeev : LibInt (2-el integral package), F12 methods Garnet Chan, S. Sharma, R. Olivares : DMRG Ulf Ekstrom : XCFun DFT Library Mihaly Kallay : mrcc (arbitrary order and MRCC methods) Andreas Klamt, Michael Diedenhofen : otool_cosmo (COSMO solvation model) Frank Weinhold : gennbo (NPA and NBO analysis) Christopher J. Cramer and Donald G. Truhlar : smd solvation model Your calculation uses the libint2 library for the computation of 2-el integrals For citations please refer to: http://libint.valeyev.net This ORCA versions uses: CBLAS interface : Fast vector & matrix operations LAPACKE interface : Fast linear algebra routines SCALAPACK package : Parallel linear algebra routines Your calculation utilizes the basis: Ahlrichs-VDZ Cite in your paper: H - Kr: A. Schaefer, H. Horn and R. Ahlrichs, J. Chem. Phys. 97, 2571 (1992). Your calculation utilizes the basis: Ahlrichs SVPalls1+f Cite in your paper: Rb - Xe: A. Schaefer, C. Huber and R. Ahlrichs, J. Chem. Phys. 100, 5829 (1994). Your calculation utilizes pol. fcns from basis: Ahlrichs polarization Cite in your paper: H - Kr: R. Ahlrichs and coworkers, unpublished ================================================================================ WARNINGS Please study these warnings very carefully! ================================================================================ Now building the actual basis set INFO : the flag for use of LIBINT has been found! ================================================================================ INPUT FILE ================================================================================ NAME = example.inp | 1> ! RHF SVP UseSym NoIter XYZfile | 2> %method SymThresh 1.0e-2 end | 3> *xyz 0 1 | 4> C -0.002822 -0.005082 -0.001782 | 5> C -0.723141 -1.252323 -0.511551 | 6> H 0.017157 0.029421 1.100049 | 7> H 1.042121 0.030085 -0.350586 | 8> H -0.495109 0.917401 -0.350838 | 9> H -0.743120 -1.286826 -1.613382 | 10> H -0.230855 -2.174806 -0.162495 | 11> H -1.768085 -1.287489 -0.162747 | 12> * | 13> | 14> ****END OF INPUT**** ================================================================================ ------------------------------------------------------------------------------ SYMMETRY HANDLING SETUP ------------------------------------------------------------------------------ ------------------ SYMMETRY DETECTION ------------------ Preparing Data ... done Detection Threshold: SymThresh ... 1.0000e-02 Point Group will now be determined: Moving molecule to center of mass ... done POINT GROUP ... D3d The coordinates will now be cleaned: Moving to standard coord frame ... done (Changed the main axis to z and one of the C2's to x) Structure cleanup requested ... yes Selected point group ... D3d Cleaning Tolerance SymThresh ... 1.0000e-02 Some missing point group data is constructed: Constructing symmetry operations ... done Creating atom transfer table ... done Creating asymmetric unit ... done Cleaning coordinates ... done ----------------------------------------------- SYMMETRY-PERFECTED CARTESIAN COORDINATES (A.U.) ----------------------------------------------- 0 C -0.00000000 -0.00000000 1.44361140 1 C -0.00000000 -0.00000000 -1.44361140 2 H 1.67796738 -0.96877492 2.20875463 3 H 0.00000000 1.93754983 2.20875463 4 H -1.67796738 -0.96877492 2.20875463 5 H -1.67796738 0.96877492 -2.20875463 6 H 1.67796738 0.96877492 -2.20875463 7 H -0.00000000 -1.93754983 -2.20875463 ------------------ SYMMETRY REDUCTION ------------------ ORCA supports only abelian point groups. It is now checked, if the determined point group is supported: Point Group ( D3d ) is ... NOT supported Reducing to abelian subgroup ... C2h (coordinate transformation was performed) (Re)building abelian point group: Creating Character Table ... done Making direct product table ... done Constructing symmetry operations ... done Creating atom transfer table ... done Creating asymmetric unit ... done ---------------------- ASYMMETRIC UNIT IN C2h ---------------------- # AT MASS COORDS (A.U.) BAS 0 C 12.0110 1.44361140 0.00000000 -0.00000000 0 2 H 1.0080 2.20875463 0.96877492 1.67796738 0 3 H 1.0080 2.20875463 -1.93754983 0.00000000 0 ---------------------- SYMMETRY ADAPTED BASIS ---------------------- The coefficients for the symmetry adapted linear combinations (SALCS) of basis functions will now be computed: Number of basis functions ... 58 Preparing memory ... done Constructing Gamma(red) ... done Reducing Gamma(red) ... done Constructing SALCs ... done Checking SALC integrity ... nothing suspicious Normalizing SALCs ... done Storing the symmetry object: Symmetry file ... example.sym.tmp Writing symmetry information ... done **************************** * Single Point Calculation * **************************** --------------------------------- CARTESIAN COORDINATES (ANGSTROEM) --------------------------------- C 0.763926 0.000000 -0.000000 C -0.763926 0.000000 -0.000000 H 1.168823 0.512654 0.887942 H 1.168823 -1.025307 0.000000 H 1.168823 0.512654 -0.887942 H -1.168823 -0.512654 -0.887942 H -1.168823 -0.512654 0.887942 H -1.168823 1.025307 -0.000000 ---------------------------- CARTESIAN COORDINATES (A.U.) ---------------------------- NO LB ZA FRAG MASS X Y Z 0 C 6.0000 0 12.011 1.443611398155389 0.000000000000000 -0.000000000000000 1 C 6.0000 0 12.011 -1.443611398155389 0.000000000000000 -0.000000000000000 2 H 1.0000 0 1.008 2.208754627743215 0.968774917357881 1.677967377962190 3 H 1.0000 0 1.008 2.208754627743215 -1.937549834715762 0.000000000000000 4 H 1.0000 0 1.008 2.208754627743215 0.968774917357880 -1.677967377962190 5 H 1.0000 0 1.008 -2.208754627743215 -0.968774917357881 -1.677967377962190 6 H 1.0000 0 1.008 -2.208754627743215 -0.968774917357880 1.677967377962190 7 H 1.0000 0 1.008 -2.208754627743215 1.937549834715761 -0.000000000000001 -------------------------------- INTERNAL COORDINATES (ANGSTROEM) -------------------------------- C 0 0 0 0.000000 0.000 0.000 C 1 0 0 1.527853 0.000 0.000 H 1 2 0 1.102552 111.563 0.000 H 1 2 3 1.102183 111.557 120.049 H 1 2 3 1.102344 111.527 239.951 H 2 1 3 1.102552 111.563 180.000 H 2 1 3 1.102343 111.527 300.049 H 2 1 3 1.102184 111.557 59.951 --------------------------- INTERNAL COORDINATES (A.U.) --------------------------- C 0 0 0 0.000000 0.000 0.000 C 1 0 0 2.887223 0.000 0.000 H 1 2 0 2.083522 111.563 0.000 H 1 2 3 2.082824 111.557 120.049 H 1 2 3 2.083128 111.527 239.951 H 2 1 3 2.083522 111.563 180.000 H 2 1 3 2.083127 111.527 300.049 H 2 1 3 2.082825 111.557 59.951 --------------------- BASIS SET INFORMATION --------------------- There are 2 groups of distinct atoms Group 1 Type C : 7s4p1d contracted to 3s2p1d pattern {511/31/1} Group 2 Type H : 4s1p contracted to 2s1p pattern {31/1} Atom 0C basis set group => 1 Atom 1C basis set group => 1 Atom 2H basis set group => 2 Atom 3H basis set group => 2 Atom 4H basis set group => 2 Atom 5H basis set group => 2 Atom 6H basis set group => 2 Atom 7H basis set group => 2 Checking for AutoStart: The File: example.gbw exists Trying to determine its content: ... Fine, the file contains calculation information ... Fine, the calculation information was read ... Fine, the file contains a basis set ... Fine, the basis set was read ... Fine, the file contains a geometry ... Fine, the geometry was read ... Fine, the file contains a set of orbitals ... Fine, the orbitals can be read => possible old guess file was deleted => GBW file was renamed to GES file => GES file is set as startup file => Guess is set to MORead ... now leaving AutoStart ------------------------------------------------------------------------------ ORCA GTO INTEGRAL CALCULATION ------------------------------------------------------------------------------ BASIS SET STATISTICS AND STARTUP INFO # of primitive gaussian shells ... 54 # of primitive gaussian functions ... 90 # of contracted shell ... 30 # of contracted basis functions ... 58 Highest angular momentum ... 2 Maximum contraction depth ... 5 Integral package used ... LIBINT Integral threshhold Thresh ... 1.000e-10 Primitive cut-off TCut ... 1.000e-11 INTEGRAL EVALUATION One electron integrals ... done Pre-screening matrix ... done Shell pair data ... done ( 0.000 sec) ------------------------------------------------------------------------------- ORCA SCF ------------------------------------------------------------------------------- ------------ SCF SETTINGS ------------ Hamiltonian: Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) General Settings: Integral files IntName .... example Hartree-Fock type HFTyp .... RHF Total Charge Charge .... 0 Multiplicity Mult .... 1 Number of Electrons NEL .... 18 Basis Dimension Dim .... 58 Nuclear Repulsion ENuc .... 41.9997165985 Eh Symmetry handling UseSym .... ON Point group .... C2h Used point group .... C2h Number of irreps .... 4 Irrep Ag has 19 symmetry adapted basis functions (ofs= 0) Irrep Bg has 10 symmetry adapted basis functions (ofs= 19) Irrep Au has 10 symmetry adapted basis functions (ofs= 29) Irrep Bu has 19 symmetry adapted basis functions (ofs= 39) Convergence Acceleration: DIIS CNVDIIS .... on Start iteration DIISMaxIt .... 12 Startup error DIISStart .... 0.200000 # of expansion vecs DIISMaxEq .... 5 Bias factor DIISBfac .... 1.050 Max. coefficient DIISMaxC .... 10.000 Newton-Raphson CNVNR .... off SOSCF CNVSOSCF .... on Start iteration SOSCFMaxIt .... 150 Startup grad/error SOSCFStart .... 0.003300 Level Shifting CNVShift .... on Level shift para. LevelShift .... 0.2500 Turn off err/grad. ShiftErr .... 0.0010 Zerner damping CNVZerner .... off Static damping CNVDamp .... on Fraction old density DampFac .... 0.7000 Max. Damping (<1) DampMax .... 0.9800 Min. Damping (>=0) DampMin .... 0.0000 Turn off err/grad. DampErr .... 0.1000 Fernandez-Rico CNVRico .... off SCF Procedure: Maximum # iterations MaxIter .... 0 SCF integral mode SCFMode .... Direct Integral package .... LIBINT Reset frequeny DirectResetFreq .... 20 Integral Threshold Thresh .... 1.000e-10 Eh Primitive CutOff TCut .... 1.000e-11 Eh Convergence Tolerance: Convergence Check Mode ConvCheckMode .... Total+1el-Energy Energy Change TolE .... 1.000e-06 Eh 1-El. energy change .... 1.000e-03 Eh Orbital Gradient TolG .... 5.000e-05 Orbital Rotation angle TolX .... 5.000e-05 DIIS Error TolErr .... 1.000e-06 Diagonalization of the overlap matrix: Smallest eigenvalue ... 4.541e-03 Time for diagonalization ... 0.006 sec Threshold for overlap eigenvalues ... 1.000e-08 Number of eigenvalues below threshold ... 0 Time for construction of square roots ... 0.004 sec Producing symmetrization matrix ... done ( 0.003 sec) Total time needed ... 0.012 sec --------------------- INITIAL GUESS: MOREAD --------------------- Guess MOs are being read from file: example.ges Input Geometry matches current geometry (good) Input basis set matches current basis set (good) Warning: Geometry matches/Basis set matches and symmetry is to be used We proceed in good trust that the input orbitals and irreps are correct MOs were renormalized MOs were reorthogonalized (Cholesky) Irrep occupations for operator 0 Ag - 4 Bg - 1 Au - 1 Bu - 3 ------------------ INITIAL GUESS DONE ( 0.0 sec) ------------------ ****MaxIter==0 has been chosen - skipping the SCF**** !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! !! SERIOUS WARNING: The orbitals and populations did NOT !! !! come from a CONVERGED calculation !! !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! THE WAVEFUNCTION AND DENSITY WILL STILL BE STORED BUT BE CAREFUL MAKE SURE THAT WHAT YOU INPUT MAKES ACTUALLY SENSE! **** DENSITY FILE WAS UPDATED (example.scfp.tmp) **** ---------------- ORBITAL ENERGIES ---------------- NO OCC E(Eh) E(eV) Irrep 0 2.0000 -9.959770 -271.0191 1-Bu 1 2.0000 -9.959496 -271.0117 1-Ag 2 2.0000 -0.814885 -22.1741 2-Ag 3 2.0000 -0.681703 -18.5501 2-Bu 4 2.0000 -0.516342 -14.0504 3-Bu 5 2.0000 -0.516208 -14.0467 1-Au 6 2.0000 -0.479307 -13.0426 3-Ag 7 2.0000 -0.425398 -11.5757 4-Ag 8 2.0000 -0.425140 -11.5686 1-Bg 9 0.0000 -0.017872 -0.4863 5-Ag 10 0.0000 0.027627 0.7518 2-Au 11 0.0000 0.028303 0.7702 4-Bu 12 0.0000 0.029762 0.8099 5-Bu 13 0.0000 0.059547 1.6204 6-Ag 14 0.0000 0.060321 1.6414 2-Bg 15 0.0000 0.074954 2.0396 6-Bu 16 0.0000 0.284122 7.7313 3-Au 17 0.0000 0.287986 7.8365 7-Bu 18 0.0000 0.296577 8.0703 7-Ag 19 0.0000 0.393204 10.6996 3-Bg 20 0.0000 0.396363 10.7856 8-Ag 21 0.0000 0.447876 12.1873 8-Bu 22 0.0000 0.499808 13.6005 9-Ag 23 0.0000 0.521417 14.1885 10-Ag 24 0.0000 0.521831 14.1997 4-Bg 25 0.0000 0.542525 14.7628 9-Bu 26 0.0000 0.545682 14.8488 4-Au 27 0.0000 0.546136 14.8611 10-Bu 28 0.0000 0.630962 17.1693 11-Ag 29 0.0000 0.842409 22.9231 11-Bu 30 0.0000 0.921897 25.0861 5-Au 31 0.0000 0.922142 25.0928 12-Bu 32 0.0000 1.191023 32.4094 5-Bg 33 0.0000 1.191361 32.4186 12-Ag 34 0.0000 1.381899 37.6034 6-Au 35 0.0000 1.386180 37.7199 6-Bg 36 0.0000 1.523638 41.4603 13-Ag 37 0.0000 1.611931 43.8629 7-Au 38 0.0000 1.612344 43.8741 7-Bg 39 0.0000 1.613207 43.8976 13-Bu 40 0.0000 1.614338 43.9284 14-Ag 41 0.0000 1.624866 44.2149 8-Au 42 0.0000 1.625506 44.2323 14-Bu 43 0.0000 1.700334 46.2684 15-Bu 44 0.0000 1.841443 50.1082 8-Bg 45 0.0000 1.841791 50.1177 15-Ag 46 0.0000 2.052773 55.8588 16-Ag 47 0.0000 2.159226 58.7555 16-Bu 48 0.0000 2.159516 58.7634 9-Au 49 0.0000 2.229882 60.6782 17-Bu 50 0.0000 2.336879 63.5897 17-Ag 51 0.0000 2.337105 63.5959 9-Bg 52 0.0000 2.427835 66.0647 18-Ag 53 0.0000 2.600461 70.7621 18-Bu 54 0.0000 2.716990 73.9331 10-Bg 55 0.0000 2.718169 73.9651 19-Ag 56 0.0000 2.788242 75.8719 10-Au 57 0.0000 2.789128 75.8960 19-Bu ******************************** * MULLIKEN POPULATION ANALYSIS * ******************************** ----------------------- MULLIKEN ATOMIC CHARGES ----------------------- 0 C : -0.543146 1 C : -0.543146 2 H : 0.181599 3 H : 0.179948 4 H : 0.181599 5 H : 0.181599 6 H : 0.181599 7 H : 0.179948 Sum of atomic charges: -0.0000000 -------------------------------- MULLIKEN REDUCED ORBITAL CHARGES -------------------------------- 0 C s : 3.131668 s : 3.131668 pz : 1.177455 p : 3.382229 px : 1.026430 py : 1.178344 dz2 : 0.004851 d : 0.029249 dxz : 0.007141 dyz : 0.004408 dx2y2 : 0.005726 dxy : 0.007123 1 C s : 3.131668 s : 3.131668 pz : 1.177455 p : 3.382229 px : 1.026430 py : 1.178344 dz2 : 0.004851 d : 0.029249 dxz : 0.007141 dyz : 0.004408 dx2y2 : 0.005726 dxy : 0.007123 2 H s : 0.791048 s : 0.791048 pz : 0.013606 p : 0.027353 px : 0.005591 py : 0.008156 3 H s : 0.792600 s : 0.792600 pz : 0.005455 p : 0.027452 px : 0.005572 py : 0.016426 4 H s : 0.791048 s : 0.791048 pz : 0.013606 p : 0.027353 px : 0.005591 py : 0.008156 5 H s : 0.791048 s : 0.791048 pz : 0.013606 p : 0.027353 px : 0.005591 py : 0.008156 6 H s : 0.791048 s : 0.791048 pz : 0.013606 p : 0.027353 px : 0.005591 py : 0.008156 7 H s : 0.792600 s : 0.792600 pz : 0.005455 p : 0.027452 px : 0.005572 py : 0.016426 ******************************* * LOEWDIN POPULATION ANALYSIS * ******************************* ---------------------- LOEWDIN ATOMIC CHARGES ---------------------- 0 C : -0.313623 1 C : -0.313623 2 H : 0.104701 3 H : 0.104221 4 H : 0.104701 5 H : 0.104701 6 H : 0.104701 7 H : 0.104221 ------------------------------- LOEWDIN REDUCED ORBITAL CHARGES ------------------------------- 0 C s : 2.884625 s : 2.884625 pz : 1.156736 p : 3.363064 px : 1.049471 py : 1.156857 dz2 : 0.012087 d : 0.065934 dxz : 0.013667 dyz : 0.009790 dx2y2 : 0.016732 dxy : 0.013658 1 C s : 2.884625 s : 2.884625 pz : 1.156736 p : 3.363064 px : 1.049471 py : 1.156857 dz2 : 0.012087 d : 0.065934 dxz : 0.013667 dyz : 0.009790 dx2y2 : 0.016732 dxy : 0.013658 2 H s : 0.813570 s : 0.813570 pz : 0.041226 p : 0.081729 px : 0.017481 py : 0.023021 3 H s : 0.813988 s : 0.813988 pz : 0.013997 p : 0.081791 px : 0.017506 py : 0.050288 4 H s : 0.813570 s : 0.813570 pz : 0.041226 p : 0.081729 px : 0.017481 py : 0.023021 5 H s : 0.813570 s : 0.813570 pz : 0.041226 p : 0.081729 px : 0.017481 py : 0.023021 6 H s : 0.813570 s : 0.813570 pz : 0.041226 p : 0.081729 px : 0.017481 py : 0.023021 7 H s : 0.813988 s : 0.813988 pz : 0.013997 p : 0.081791 px : 0.017506 py : 0.050288 ***************************** * MAYER POPULATION ANALYSIS * ***************************** NA - Mulliken gross atomic population ZA - Total nuclear charge QA - Mulliken gross atomic charge VA - Mayer's total valence BVA - Mayer's bonded valence FA - Mayer's free valence ATOM NA ZA QA VA BVA FA 0 C 6.5431 6.0000 -0.5431 3.9975 3.9975 -0.0000 1 C 6.5431 6.0000 -0.5431 3.9975 3.9975 -0.0000 2 H 0.8184 1.0000 0.1816 0.9662 0.9662 0.0000 3 H 0.8201 1.0000 0.1799 0.9665 0.9665 -0.0000 4 H 0.8184 1.0000 0.1816 0.9662 0.9662 -0.0000 5 H 0.8184 1.0000 0.1816 0.9662 0.9662 -0.0000 6 H 0.8184 1.0000 0.1816 0.9662 0.9662 0.0000 7 H 0.8201 1.0000 0.1799 0.9665 0.9665 -0.0000 Mayer bond orders larger than 0.1 B( 0-C , 1-C ) : 1.1416 B( 0-C , 2-H ) : 0.9454 B( 0-C , 3-H ) : 0.9458 B( 0-C , 4-H ) : 0.9454 B( 1-C , 5-H ) : 0.9454 B( 1-C , 6-H ) : 0.9454 B( 1-C , 7-H ) : 0.9458 ------- TIMINGS ------- Total SCF time: 0 days 0 hours 0 min 0 sec Total time .... 0.021 sec Sum of individual times .... 0.044 sec (213.3%) Fock matrix formation .... 0.000 sec ( 0.0%) Diagonalization .... 0.000 sec ( 0.0%) Density matrix formation .... 0.000 sec ( 0.0%) Population analysis .... 0.014 sec ( 65.4%) Initial guess .... 0.031 sec (148.0%) Orbital Transformation .... 0.000 sec ( 0.0%) Orbital Orthonormalization .... 0.030 sec (142.6%) DIIS solution .... 0.000 sec ( 0.0%) SOSCF solution .... 0.000 sec ( 0.0%) ------------------------- -------------------- FINAL SINGLE POINT ENERGY 0.000000000000 ------------------------- -------------------- *************************************** * ORCA property calculations * *************************************** --------------------- Active property flags --------------------- (+) Dipole Moment ------------------------------------------------------------------------------ ORCA ELECTRIC PROPERTIES CALCULATION ------------------------------------------------------------------------------ Dipole Moment Calculation ... on Quadrupole Moment Calculation ... off Polarizability Calculation ... off GBWName ... example.gbw Electron density file ... example.scfp.tmp ------------- DIPOLE MOMENT ------------- X Y Z Electronic contribution: -0.00000 -0.00000 0.00000 Nuclear contribution : 0.00000 -0.00000 -0.00000 ----------------------------------------- Total Dipole Moment : -0.00000 -0.00000 0.00000 ----------------------------------------- Magnitude (a.u.) : 0.00000 Magnitude (Debye) : 0.00000 Timings for individual modules: Sum of individual times ... 8.094 sec (= 0.135 min) GTO integral calculation ... 3.966 sec (= 0.066 min) 49.0 % SCF iterations ... 4.128 sec (= 0.069 min) 51.0 % ****ORCA TERMINATED NORMALLY**** TOTAL RUN TIME: 0 days 0 hours 0 minutes 11 seconds 867 msec