***************** * O R C A * ***************** #, ### #### ##### ###### ########, ,,################,,,,, ,,#################################,, ,,##########################################,, ,#########################################, ''#####, ,#############################################,, '####, ,##################################################,,,,####, ,###########'''' ''''############################### ,#####'' ,,,,##########,,,, '''####''' '#### ,##' ,,,,###########################,,, '## ' ,,###'''' '''############,,, ,,##'' '''############,,,, ,,,,,,###'' ,#'' '''#######################''' ' ''''####'''' ,#######, #######, ,#######, ## ,#' '#, ## ## ,#' '#, #''# ,####, ,####, ## ## ## ,#' ## #' '# #' #' '# ## ## ####### ## ,######, #####, # # '#, ,#' ## ## '#, ,#' ,# #, #, # #, ,# '#######' ## ## '#######' #' '# '####' # '####' ######################################################### # -***- # # Department of theory and spectroscopy # # # # Frank Neese # # # # Directorship, Architecture, Infrastructure # # SHARK, DRIVERS # # Core code/Algorithms in most modules # # # # Max Planck Institute fuer Kohlenforschung # # Kaiser Wilhelm Platz 1 # # D-45470 Muelheim/Ruhr # # Germany # # # # All rights reserved # # -***- # ######################################################### Program Version 6.0.1 - RELEASE - With contributions from (in alphabetic order): [Max-Planck-Institut fuer Kohlenforschung] Daniel Aravena : Magnetic Suceptibility Michael Atanasov : Ab Initio Ligand Field Theory (pilot matlab implementation) Alexander A. Auer : GIAO ZORA, VPT2 properties, NMR spectrum Ute Becker : All parallelization in ORCA, NUMFREQ, NUMCALC Giovanni Bistoni : ED, misc. LED, open-shell LED, HFLD Martin Brehm : Molecular dynamics Dmytro Bykov : pre 5.0 version of the SCF Hessian Marcos Casanova-Páez : Triplet and SCS-CIS(D). UHF-(DLPNO)-IP/EA/STEOM-CCSD. UHF-CVS-IP/STEOM-CCSD Vijay G. Chilkuri : MRCI spin determinant printing, contributions to CSF-ICE Pauline Colinet : FMM embedding Dipayan Datta : RHF DLPNO-CCSD density Achintya Kumar Dutta : EOM-CC, STEOM-CC Nicolas Foglia : Exact transition moments, OPA infrastructure, MCD improvements Dmitry Ganyushin : Spin-Orbit,Spin-Spin,Magnetic field MRCI Miquel Garcia-Rates : C-PCM and meta-GGA Hessian, CCSD/C-PCM, Gaussian charge scheme Tiago L. C. Gouveia : GS-ROHF, GS-ROCIS Yang Guo : DLPNO-NEVPT2, F12-NEVPT2, CIM, IAO-localization Andreas Hansen : Spin unrestricted coupled pair/coupled cluster methods Ingolf Harden : AUTO-CI MPn and infrastructure Benjamin Helmich-Paris : MC-RPA, TRAH-(SCF,CASSCF), AVAS, COSX integrals, SCF dyn. polar. Lee Huntington : MR-EOM, pCC Robert Izsak : Overlap fitted RIJCOSX, COSX-SCS-MP3, EOM Riya Kayal : Wick's Theorem for AUTO-CI, AUTO-CI UHF-CCSDT Emily Kempfer : AUTO-CI, RHF CISDT and CCSDT Christian Kollmar : KDIIS, OOCD, Brueckner-CCSD(T), CCSD density, CASPT2, CASPT2-K, improved NEVPT2 Axel Koslowski : Symmetry handling Simone Kossmann : meta-GGA functionals, TD-DFT gradient, OOMP2, (MP2 Hessian; deprecated post 5.0) Lucas Lang : DCDCAS Marvin Lechner : AUTO-CI (C++ implementation), FIC-MRCC Spencer Leger : CASSCF response Dagmar Lenk : GEPOL surface, SMD, ORCA-2-JSON Dimitrios Liakos : Extrapolation schemes; Compound Job, initial MDCI parallelization Dimitrios Manganas : Further ROCIS development; embedding schemes. LFT, Crystal Embedding Dimitrios Pantazis : SARC Basis sets Anastasios Papadopoulos: AUTO-CI, single reference methods and gradients Taras Petrenko : pre 6.0 DFT Hessian and TD-DFT gradient, (ASA, deprecated), ECA, 1-Electron XAS/XES, NRVS Peter Pinski : DLPNO-MP2, DLPNO-MP2 Gradient Christoph Reimann : Effective Core Potentials Marius Retegan : Local ZFS, SOC Christoph Riplinger : Optimizer, TS searches, QM/MM, DLPNO-CCSD(T), (RO)-DLPNO pert. Triples Michael Roemelt : Original ROCIS implementation Masaaki Saitow : Open-shell DLPNO-CCSD energy and density Barbara Sandhoefer : DKH picture change effects Kantharuban Sivalingam : CASSCF convergence/infrastructure, NEVPT2 and variants, FIC-MRCI Bernardo de Souza : ESD, SOC TD-DFT Georgi L. Stoychev : AutoAux, RI-MP2 NMR, DLPNO-MP2 response, X2C Van Anh Tran : RI-MP2 g-tensors Willem Van den Heuvel : Paramagnetic NMR Zikuan Wang : NOTCH, Electric field optimization Frank Wennmohs : Technical directorship and infrastructure Hang Xu : AUTO-CI-Response properties [FACCTs GmbH] Markus Bursch, Miquel Garcia-Rates, Christoph Riplinger, Bernardo de Souza, Georgi L. Stoychev APM, Basis sets (HGBS, AHGBS, def-TZVP (Ac-Lr), def2-XVPD (La-Lu)), CI-OPT, improved COSX, DLPNO-Multilevel, DOCKER, DRACO, updates on ESD, GOAT, IRC, LR-CPCM, MBIS, meta-GGA TD-DFT gradient, ML-optimized integration grids, MM, NACMEs, nearIR, NEB, NEB-TS, NL-DFT gradient (VV10), 2- and 3-layer-ONIOM, interface openCOSMO-RS, QMMM, Crystal-QMMM, SF, symmetry and pop. for TD-DFT, r2SCAN hybrids, SOLVATOR [Other institutions] V. Asgeirsson : NEB Christoph Bannwarth : sTDA-DFT, sTD-DFT, PBEh-3c, B97-3c, D3 Sebastian Ehlert : rSCAN, r2SCAN, r2SCAN-3c, D4, dhf basis sets Marvin Friede : D4 for Fr, Ra, Ac-Lr Lars Goerigk : TD-DFT with DH, B97 family of functionals Stefan Grimme : VdW corrections, initial TS optimization, DFT functionals, gCP, sTDA/sTD-DF Waldemar Hujo : DFT-NL H. Jonsson : NEB Holger Kruse : gCP Marcel Mueller : wB97X-3c, vDZP basis set Hagen Neugebauer : wr2SCAN Tobias Risthaus : range-separated hybrid DFT Lukas Wittmann : regularized MP2, r2SCAN double-hybrids, wr2SCAN We gratefully acknowledge several colleagues who have allowed us to interface, adapt or use parts of their codes: Ed Valeev, F. Pavosevic, A. Kumar : LibInt (2-el integral package), F12 methods Garnet Chan, S. Sharma, J. Yang, R. Olivares : DMRG Ulf Ekstrom : XCFun DFT Library Mihaly Kallay : mrcc (arbitrary order and MRCC methods) Frank Weinhold : gennbo (NPA and NBO analysis) Simon Mueller : openCOSMO-RS Christopher J. Cramer and Donald G. Truhlar : smd solvation model S Lehtola, MJT Oliveira, MAL Marques : LibXC Library Liviu Ungur et al : ANISO software Your calculation uses the libint2 library for the computation of 2-el integrals For citations please refer to: http://libint.valeyev.net Your ORCA version has been built with support for libXC version: 6.2.2 For citations please refer to: https://libxc.gitlab.io This ORCA versions uses: CBLAS interface : Fast vector & matrix operations LAPACKE interface : Fast linear algebra routines SCALAPACK package : Parallel linear algebra routines Shared memory : Shared parallel matrices BLAS/LAPACK : OpenBLAS 0.3.27 USE64BITINT DYNAMIC_ARCH NO_AFFINITY SkylakeX SINGLE_THREADED Core in use : SkylakeX Copyright (c) 2011-2014, The OpenBLAS Project NOTE: MaxCore=3000 MB was set to SCF,MP2,MDCI,CIPSI,MRCI and CIS => If you want to overwrite this, your respective input block should be placed after the MaxCore statement *************************************** The coordinates will be read from file: nitrochlorobenz.xyz *************************************** Your calculation utilizes the SMD solvation module Please cite in your paper: A.V. Marenich, C.J. Cramer, D.G. Truhlar J. Phys. Chem. B, 113, (2009), 6378 XCFun DFT library Copyright 2009-2010 Ulf Ekstrom and contributors. See http://admol.org/xcfun for more information. This is free software; see the source code for copying conditions. There is ABSOLUTELY NO WARRANTY; not even for MERCHANTABILITY or FITNESS FOR A PARTICULAR PURPOSE. For details see the documentation. Scientific users of this library should cite U. Ekstrom, L. Visscher, R. Bast, A. J. Thorvaldsen and K. Ruud; J.Chem.Theor.Comp. 2010, DOI: 10.1021/ct100117s XCFun Version 0.99 Warning: RI is on but no J-basis has been assigned. Assigning Def2/J (nothing to worry about!) ================================================================================ ----- Orbital basis set information ----- Your calculation utilizes the basis: def2-TZVPP F. Weigend and R. Ahlrichs, Phys. Chem. Chem. Phys. 7, 3297 (2005). ----- AuxJ basis set information ----- Your calculation utilizes the auxiliary basis: def2/J F. Weigend, Phys. Chem. Chem. Phys. 8, 1057 (2006). ================================================================================ WARNINGS Please study these warnings very carefully! ================================================================================ WARNING: Functional chosen is sensitive to the integration grid. DEFGRID3 seems to be a minimum grid for robust results! INFO : Checking CIS options ... WARNING: CIS/ROCIS methods need fully converged wavefunctions ===> : Setting SCFConvForced true You can overwrite this default with %scf ConvForced false ================================================================================ INPUT FILE ================================================================================ NAME = nitrochlorobenz.inp | 1> ! M062X def2-tzvpp SMD(acetonitrile) | 2> %TDDFT | 3> nroots 3 | 4> end | 5> %pal | 6> nproc 4 | 7> end | 8> %maxcore 3000 | 9> *xyzfile 0 1 nitrochlorobenz.xyz | 10> | 11> | 12> ****END OF INPUT**** ================================================================================ **************************** * Single Point Calculation * **************************** --------------------------------- CARTESIAN COORDINATES (ANGSTROEM) --------------------------------- C 0.316297 -0.046046 -2.141657 C -0.832032 -0.394994 -1.453986 C 1.425994 0.426633 -1.460309 H -1.708141 -0.765740 -1.962864 H 2.321825 0.699180 -1.995406 C -0.851789 -0.262885 -0.071756 C 1.387591 0.552186 -0.076376 Cl 2.769198 1.140451 0.768156 C 0.248210 0.208795 0.631755 H 0.200219 0.298456 1.706014 H 0.349975 -0.141887 -3.215492 N -2.047305 -0.625092 0.659700 O -2.989668 -1.034758 0.019534 O -2.029158 -0.495729 1.862823 ---------------------------- CARTESIAN COORDINATES (A.U.) ---------------------------- NO LB ZA FRAG MASS X Y Z 0 C 6.0000 0 12.011 0.597715 -0.087014 -4.047145 1 C 6.0000 0 12.011 -1.572313 -0.746430 -2.747634 2 C 6.0000 0 12.011 2.694739 0.806220 -2.759585 3 H 1.0000 0 1.008 -3.227918 -1.447039 -3.709276 4 H 1.0000 0 1.008 4.387614 1.321258 -3.770771 5 C 6.0000 0 12.011 -1.609648 -0.496780 -0.135599 6 C 6.0000 0 12.011 2.622166 1.043481 -0.144330 7 Cl 17.0000 0 35.453 5.233027 2.155140 1.451605 8 C 6.0000 0 12.011 0.469048 0.394565 1.193844 9 H 1.0000 0 1.008 0.378359 0.563999 3.223899 10 H 1.0000 0 1.008 0.661356 -0.268128 -6.076400 11 N 7.0000 0 14.007 -3.868846 -1.181253 1.246652 12 O 8.0000 0 15.999 -5.649654 -1.955409 0.036913 13 O 8.0000 0 15.999 -3.834554 -0.936792 3.520225 -------------------------------- INTERNAL COORDINATES (ANGSTROEM) -------------------------------- C 0 0 0 0.000000000000 0.00000000 0.00000000 C 1 0 0 1.383227322793 0.00000000 0.00000000 C 1 2 0 1.385311080317 120.43584368 0.00000000 H 2 1 3 1.078877313718 121.75926441 180.02855206 H 3 1 2 1.078481608721 120.50277766 180.01087731 C 2 1 3 1.388669061243 118.85901879 0.00000000 C 3 1 2 1.390147183852 119.88928883 0.00000000 Cl 7 3 1 1.722826440456 119.78159526 180.00517875 C 7 3 1 1.384758736638 120.62540617 0.00000000 H 9 7 3 1.079062007003 121.67414850 179.93117435 H 1 2 3 1.078630021147 119.89714425 179.99894229 N 6 2 1 1.447577260386 119.39969740 180.02061882 O 12 6 2 1.210655383317 117.40857142 0.07596479 O 12 6 2 1.210194232956 117.59466453 180.07419806 --------------------------- INTERNAL COORDINATES (A.U.) --------------------------- C 0 0 0 0.000000000000 0.00000000 0.00000000 C 1 0 0 2.613920821036 0.00000000 0.00000000 C 1 2 0 2.617858552086 120.43584368 0.00000000 H 2 1 3 2.038782655028 121.75926441 180.02855206 H 3 1 2 2.038034880953 120.50277766 180.01087731 C 2 1 3 2.624204216398 118.85901879 0.00000000 C 3 1 2 2.626997463323 119.88928883 0.00000000 Cl 7 3 1 3.255670148739 119.78159526 180.00517875 C 7 3 1 2.616814773802 120.62540617 0.00000000 H 9 7 3 2.039131674754 121.67414850 179.93117435 H 1 2 3 2.038315339794 119.89714425 179.99894229 N 6 2 1 2.735524579822 119.39969740 180.02061882 O 12 6 2 2.287807117026 117.40857142 0.07596479 O 12 6 2 2.286935669138 117.59466453 180.07419806 --------------------- BASIS SET INFORMATION --------------------- There are 5 groups of distinct atoms Group 1 Type C : 11s6p2d1f contracted to 5s3p2d1f pattern {62111/411/11/1} Group 2 Type H : 5s2p1d contracted to 3s2p1d pattern {311/11/1} Group 3 Type Cl : 14s9p3d1f contracted to 5s5p3d1f pattern {73211/51111/111/1} Group 4 Type N : 11s6p2d1f contracted to 5s3p2d1f pattern {62111/411/11/1} Group 5 Type O : 11s6p2d1f contracted to 5s3p2d1f pattern {62111/411/11/1} Atom 0C basis set group => 1 Atom 1C basis set group => 1 Atom 2C basis set group => 1 Atom 3H basis set group => 2 Atom 4H basis set group => 2 Atom 5C basis set group => 1 Atom 6C basis set group => 1 Atom 7Cl basis set group => 3 Atom 8C basis set group => 1 Atom 9H basis set group => 2 Atom 10H basis set group => 2 Atom 11N basis set group => 4 Atom 12O basis set group => 5 Atom 13O basis set group => 5 --------------------------------- AUXILIARY/J BASIS SET INFORMATION --------------------------------- There are 5 groups of distinct atoms Group 1 Type C : 12s5p4d2f1g contracted to 6s4p3d1f1g pattern {711111/2111/211/2/1} Group 2 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} Group 3 Type Cl : 14s5p5d2f1g contracted to 8s4p3d1f1g pattern {71111111/2111/311/2/1} Group 4 Type N : 12s5p4d2f1g contracted to 6s4p3d1f1g pattern {711111/2111/211/2/1} Group 5 Type O : 12s5p4d2f1g contracted to 6s4p3d1f1g pattern {711111/2111/211/2/1} Atom 0C basis set group => 1 Atom 1C basis set group => 1 Atom 2C basis set group => 1 Atom 3H basis set group => 2 Atom 4H basis set group => 2 Atom 5C basis set group => 1 Atom 6C basis set group => 1 Atom 7Cl basis set group => 3 Atom 8C basis set group => 1 Atom 9H basis set group => 2 Atom 10H basis set group => 2 Atom 11N basis set group => 4 Atom 12O basis set group => 5 Atom 13O basis set group => 5 ************************************************************ * Program running with 4 parallel MPI-processes * * working on a common directory * ************************************************************ ------------------------------------------------------------------------------ ORCA STARTUP CALCULATIONS -- RI-GTO INTEGRALS CHOSEN -- ------------------------------------------------------------------------------ ------------------------------------------------------------------------------ ___ / \ - P O W E R E D B Y - / \ | | | _ _ __ _____ __ __ | | | | | | | / \ | _ \ | | / | \ \/ | | | | / \ | | | | | | / / / \ \ | |__| | / /\ \ | |_| | | |/ / | | | | __ | / /__\ \ | / | \ | | | | | | | | __ | | \ | |\ \ \ / | | | | | | | | | |\ \ | | \ \ \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ - O R C A' S B I G F R I E N D - & - I N T E G R A L F E E D E R - v1 FN, 2020, v2 2021, v3 2022-2024 ------------------------------------------------------------------------------ ---------------------- SHARK INTEGRAL PACKAGE ---------------------- Number of atoms ... 14 Number of basis functions ... 377 Number of shells ... 137 Maximum angular momentum ... 3 Integral batch strategy ... SHARK/LIBINT Hybrid RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) Printlevel ... 1 Contraction scheme used ... SEGMENTED contraction Prescreening option ... SCHWARTZ Thresh ... 1.000e-10 Tcut ... 1.000e-11 Tpresel ... 1.000e-11 Coulomb Range Separation ... NOT USED Exchange Range Separation ... NOT USED Multipole approximations ... NOT USED Finite Nucleus Model ... NOT USED CABS basis ... NOT available Auxiliary Coulomb fitting basis ... AVAILABLE # of basis functions in Aux-J ... 536 # of shells in Aux-J ... 172 Maximum angular momentum in Aux-J ... 4 Auxiliary J/K fitting basis ... NOT available Auxiliary Correlation fitting basis ... NOT available Auxiliary 'external' fitting basis ... NOT available Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 137 Check shell pair data ... done ( 0.0 sec) Shell pair information Shell pair cut-off parameter TPreSel ... 1.0e-11 Total number of shell pairs ... 9453 Shell pairs after pre-screening ... 8106 Total number of primitive shell pairs ... 28925 Primitive shell pairs kept ... 18140 la=0 lb=0: 1592 shell pairs la=1 lb=0: 2177 shell pairs la=1 lb=1: 751 shell pairs la=2 lb=0: 1293 shell pairs la=2 lb=1: 879 shell pairs la=2 lb=2: 275 shell pairs la=3 lb=0: 518 shell pairs la=3 lb=1: 358 shell pairs la=3 lb=2: 215 shell pairs la=3 lb=3: 48 shell pairs Calculating one electron integrals ... done ( 0.0 sec) Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 562.135857679135 Eh Diagonalization of the overlap matrix: Smallest eigenvalue ... 9.197e-06 Time for diagonalization ... 0.020 sec Threshold for overlap eigenvalues ... 1.000e-07 Number of eigenvalues below threshold ... 0 Time for construction of square roots ... 0.009 sec Total time needed ... 0.031 sec ------------------- DFT GRID GENERATION ------------------- General Integration Accuracy IntAcc ... 4.388 Radial Grid Type RadialGrid ... OptM3 with GC (2021) Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) Angular grid pruning method GridPruning ... 4 (adaptive) Weight generation scheme WeightScheme... mBecke (2022) Basis function cutoff BFCut ... 1.0000e-10 Integration weight cutoff WCut ... 1.0000e-14 Partially contracted basis set ... off Rotationally invariant grid construction ... off Angular grids for H and He will be reduced by one unit Total number of grid points ... 74477 Total number of batches ... 1171 Average number of points per batch ... 63 Average number of grid points per atom ... 5320 -------------------- COSX GRID GENERATION -------------------- GRIDX 1 ------- General Integration Accuracy IntAcc ... 3.816 Radial Grid Type RadialGrid ... OptM3 with GC (2021) Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) Angular grid pruning method GridPruning ... 4 (adaptive) Weight generation scheme WeightScheme... mBecke (2022) Basis function cutoff BFCut ... 1.0000e-10 Integration weight cutoff WCut ... 1.0000e-14 Partially contracted basis set ... on Rotationally invariant grid construction ... off Angular grids for H and He will be reduced by one unit Total number of grid points ... 10480 Total number of batches ... 89 Average number of points per batch ... 117 Average number of grid points per atom ... 749 UseSFitting ... on GRIDX 2 ------- General Integration Accuracy IntAcc ... 4.020 Radial Grid Type RadialGrid ... OptM3 with GC (2021) Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) Angular grid pruning method GridPruning ... 4 (adaptive) Weight generation scheme WeightScheme... mBecke (2022) Basis function cutoff BFCut ... 1.0000e-10 Integration weight cutoff WCut ... 1.0000e-14 Partially contracted basis set ... on Rotationally invariant grid construction ... off Angular grids for H and He will be reduced by one unit Total number of grid points ... 21309 Total number of batches ... 173 Average number of points per batch ... 123 Average number of grid points per atom ... 1522 UseSFitting ... on GRIDX 3 ------- General Integration Accuracy IntAcc ... 4.338 Radial Grid Type RadialGrid ... OptM3 with GC (2021) Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) Angular grid pruning method GridPruning ... 4 (adaptive) Weight generation scheme WeightScheme... mBecke (2022) Basis function cutoff BFCut ... 1.0000e-10 Integration weight cutoff WCut ... 1.0000e-14 Partially contracted basis set ... on Rotationally invariant grid construction ... off Angular grids for H and He will be reduced by one unit Total number of grid points ... 47561 Total number of batches ... 378 Average number of points per batch ... 125 Average number of grid points per atom ... 3397 UseSFitting ... on Initializing property integral containers ... done ( 0.0 sec) SHARK setup successfully completed in 1.5 seconds Maximum memory used throughout the entire STARTUP-calculation: 32.5 MB ************************************************************ * Program running with 4 parallel MPI-processes * * working on a common directory * ************************************************************ ------------------------------------------------------------------------------- ORCA GUESS Start orbitals & Density for SCF / CASSCF ------------------------------------------------------------------------------- ------------ SCF SETTINGS ------------ Hamiltonian: Density Functional Method .... DFT(GTOs) Exchange Functional Exchange .... M062X Correlation Functional Correlation .... M062X Gradients option PostSCFGGA .... off Hybrid DFT is turned on Fraction HF Exchange ScalHFX .... 0.540000 Scaling of DF-GGA-X ScalDFX .... 0.460000 Scaling of DF-GGA-C ScalDFC .... 1.000000 Scaling of DF-LDA-C ScalLDAC .... 1.000000 Perturbative correction .... 0.000000 RI-approximation to the Coulomb term is turned on Number of AuxJ basis functions .... 536 RIJ-COSX (HFX calculated with COS-X)).... on General Settings: Integral files IntName .... nitrochlorobenz Hartree-Fock type HFTyp .... RHF Total Charge Charge .... 0 Multiplicity Mult .... 1 Number of Electrons NEL .... 80 Basis Dimension Dim .... 377 Nuclear Repulsion ENuc .... 562.1358576791 Eh Convergence Acceleration: AO-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 MO-DIIS CNVKDIIS .... off Trust-Rad. Augm. Hess. CNVTRAH .... auto Auto Start mean grad. ratio tolernc. .... 1.125000 Auto Start start iteration .... 50 Auto Start num. interpolation iter. .... 10 Max. Number of Micro iterations .... 24 Max. Number of Macro iterations .... Maxiter - #DIIS iter Number of Davidson start vectors .... 2 Converg. threshold (grad. norm) .... 5.000e-05 Grad. Scal. Fac. for Micro threshold .... 0.100 Minimum threshold for Micro iter. .... 1.000e-02 NR start threshold (gradient norm) .... 1.000e-04 Initial trust radius .... 0.400 Minimum AH scaling param. (alpha) .... 1.000 Maximum AH scaling param. (alpha) .... 1000.000 Quad. conv. algorithm .... NR White noise on init. David. guess .... on Maximum white noise .... 0.010 Pseudo random numbers .... off Inactive MOs .... canonical Orbital update algorithm .... Taylor Preconditioner .... Diag Full preconditioner red. dimension .... 250 SOSCF CNVSOSCF .... on Start iteration SOSCFMaxIt .... 150 Startup grad/error SOSCFStart .... 0.003300 Hessian update SOSCFHessUp .... L-BFGS 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 SCF Procedure: Maximum # iterations MaxIter .... 125 SCF integral mode SCFMode .... Direct Integral package .... SHARK and LIBINT hybrid scheme Reset frequency 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 Convergence forced ConvForced .... 1 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 ------------------------------ INITIAL GUESS: MODEL POTENTIAL ------------------------------ Loading Hartree-Fock densities ... done Calculating cut-offs ... done Initializing the effective Hamiltonian ... done Setting up the integral package (SHARK) ... done Starting the Coulomb interaction ... done ( 0.1 sec) Making the grid ... done ( 0.1 sec) Mapping shells ... done Starting the XC term evaluation ... done ( 0.2 sec) promolecular density results # of electrons = 79.998058255 EX = -82.132138987 EC = -2.806959244 EX+EC = -84.939098231 Transforming the Hamiltonian ... done ( 0.0 sec) Diagonalizing the Hamiltonian ... done ( 0.0 sec) Back transforming the eigenvectors ... done ( 0.0 sec) Now organizing SCF variables ... done ------------------ INITIAL GUESS DONE ( 0.5 sec) ------------------ **** ENERGY FILE WAS UPDATED (nitrochlorobenz.en.tmp) **** Finished Guess after 0.8 sec Maximum memory used throughout the entire GUESS-calculation: 23.7 MB ************************************************************ * Program running with 4 parallel MPI-processes * * working on a common directory * ************************************************************ ------------------------------------------------------------------------------------------- ORCA LEAN-SCF memory conserving SCF solver ------------------------------------------------------------------------------------------- -------------------- CPCM SOLVATION MODEL -------------------- CPCM parameters: Epsilon ... 35.6880 Refrac ... 1.3442 Rsolv ... 1.3000 Surface type ... GAUSSIAN VDW Discretization scheme ... Constant charge density Threshold for H atoms ... 5.0000 (charges/Ang^2) Threshold for non-H atoms ... 5.0000 (charges/Ang^2) Epsilon function type ... CPCM Solvent: ... ACETONITRILE SMD-CDS solvent descriptors: Soln ... 1.3442 Soln25 ... 1.3416 Sola ... 0.0700 Solb ... 0.3200 Solg ... 41.2500 Solc ... 0.0000 Solh ... 0.0000 Radii: Scheme ... Element-dependent radii Radius for C used is 3.4960 Bohr (= 1.8500 Ang.) Radius for H used is 2.2677 Bohr (= 1.2000 Ang.) Radius for Cl used is 4.4975 Bohr (= 2.3800 Ang.) Radius for N used is 3.5716 Bohr (= 1.8900 Ang.) Radius for O used is 4.0969 Bohr (= 2.1680 Ang.) Calculating surface ... done! ( 0.0s) Cavity surface points ... 1361 Cavity Volume ... 1257.5930 Cavity Surface-area ... 690.7664 Calculating surface distance matrix ... done! ( 0.0s) Performing Cholesky decomposition & store ... done! ( 0.0s) Overall time for CPCM initialization ... 0.1s ----------------------------------------D-I-I-S-------------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) ------------------------------------------------------------------------------------------- *** Starting incremental Fock matrix formation *** 1 -896.1071352794648419 0.00e+00 1.38e-03 4.01e-02 2.33e-01 0.700 5.5 2 -896.2147292376099585 -1.08e-01 1.09e-03 3.69e-02 9.68e-02 0.700 3.3 ***Turning on AO-DIIS*** 3 -896.2616240530777532 -4.69e-02 6.87e-04 2.52e-02 4.31e-02 0.700 3.2 4 -896.2903022292056221 -2.87e-02 1.64e-03 7.49e-02 3.01e-02 0.000 3.1 5 -896.3533953771867573 -6.31e-02 2.16e-04 1.15e-02 5.18e-03 0.000 3.2 *** Initializing SOSCF *** ---------------------------------------S-O-S-C-F-------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) -------------------------------------------------------------------------------------- 6 -896.3535979675774570 -2.03e-04 8.31e-05 3.52e-03 1.75e-03 3.0 *** Restarting incremental Fock matrix formation *** 7 -896.3536152517837081 -1.73e-05 6.15e-05 2.27e-03 5.27e-04 5.4 8 -896.3536247536918609 -9.50e-06 4.01e-05 1.70e-03 2.60e-04 4.2 9 -896.3536252917739375 -5.38e-07 1.40e-05 3.80e-04 3.09e-04 4.0 **** Energy Check signals convergence **** ***************************************************** * SUCCESS * * SCF CONVERGED AFTER 9 CYCLES * ***************************************************** Recomputing exchange energy using gridx3 ... done ( 7.583 sec) Old exchange energy : -44.880775851 Eh New exchange energy : -44.880774357 Eh Exchange energy change after final integration : 0.000001494 Eh Total energy after final integration : -896.353623798 Eh SMD CDS free energy correction energy : -1.69511 Kcal/mol Total Energy after SMD CDS correction = -896.356325130 Eh **** ENERGY FILE WAS UPDATED (nitrochlorobenz.en.tmp) **** ---------------- TOTAL SCF ENERGY ---------------- Total Energy : -896.35632513045971 Eh -24391.09563 eV Components: Nuclear Repulsion : 562.13585767913457 Eh 15296.49435 eV Electronic Energy : -1458.47807481191603 Eh -39687.20607 eV One Electron Energy: -2342.92897498233833 Eh -63754.33862 eV Two Electron Energy: 884.45090017042230 Eh 24067.13254 eV CPCM Dielectric : -0.01140815899254 Eh -0.31043 eV SMD CDS (Gcds) : -0.00270133266018 Eh -0.07351 eV Virial components: Potential Energy : -1790.43227837300492 Eh -48720.13918 eV Kinetic Energy : 894.07595324254521 Eh 24329.04355 eV Virial Ratio : 2.00255053486188 DFT components: N(Alpha) : 39.999987298313 electrons N(Beta) : 39.999987298313 electrons N(Total) : 79.999974596626 electrons E(XC) : -41.350102153843 Eh CPCM Solvation Model Properties: Surface-charge : -0.01691222244117 Corrected charge : 0.00000000000000 Outlying charge corr. : 0.00001916638341 Eh 0.00052 eV Free-energy (cav+disp) : -0.00270133266018 Eh -0.07351 eV --------------- SCF CONVERGENCE --------------- Last Energy change ... 5.3808e-07 Tolerance : 1.0000e-06 Last MAX-Density change ... 3.7963e-04 Tolerance : 1.0000e-05 Last RMS-Density change ... 1.4046e-05 Tolerance : 1.0000e-06 Last DIIS Error ... 1.7483e-03 Tolerance : 1.0000e-06 Last Orbital Gradient ... 3.0943e-04 Tolerance : 5.0000e-05 Last Orbital Rotation ... 4.6177e-04 Tolerance : 5.0000e-05 ---------------- ORBITAL ENERGIES ---------------- NO OCC E(Eh) E(eV) 0 2.0000 -102.658140 -2793.4700 1 2.0000 -19.672904 -535.3269 2 2.0000 -19.672586 -535.3183 3 2.0000 -15.010604 -408.4593 4 2.0000 -10.619705 -288.9769 5 2.0000 -10.611419 -288.7514 6 2.0000 -10.575436 -287.7722 7 2.0000 -10.568564 -287.5852 8 2.0000 -10.568326 -287.5788 9 2.0000 -10.562218 -287.4126 10 2.0000 -9.820630 -267.2329 11 2.0000 -7.542589 -205.2443 12 2.0000 -7.537682 -205.1108 13 2.0000 -7.537559 -205.1074 14 2.0000 -1.387153 -37.7464 15 2.0000 -1.198975 -32.6258 16 2.0000 -1.021635 -27.8001 17 2.0000 -0.971095 -26.4248 18 2.0000 -0.910124 -24.7657 19 2.0000 -0.853556 -23.2264 20 2.0000 -0.805599 -21.9215 21 2.0000 -0.712425 -19.3861 22 2.0000 -0.690724 -18.7956 23 2.0000 -0.652849 -17.7649 24 2.0000 -0.644256 -17.5311 25 2.0000 -0.619877 -16.8677 26 2.0000 -0.590259 -16.0618 27 2.0000 -0.557660 -15.1747 28 2.0000 -0.532569 -14.4919 29 2.0000 -0.514381 -13.9970 30 2.0000 -0.488875 -13.3030 31 2.0000 -0.455852 -12.4044 32 2.0000 -0.437491 -11.9047 33 2.0000 -0.419586 -11.4175 34 2.0000 -0.408710 -11.1216 35 2.0000 -0.397246 -10.8096 36 2.0000 -0.396903 -10.8003 37 2.0000 -0.387644 -10.5483 38 2.0000 -0.340321 -9.2606 39 2.0000 -0.317438 -8.6379 40 0.0000 -0.062330 -1.6961 41 0.0000 -0.000706 -0.0192 42 0.0000 0.036117 0.9828 43 0.0000 0.064477 1.7545 44 0.0000 0.105034 2.8581 45 0.0000 0.117826 3.2062 46 0.0000 0.129843 3.5332 47 0.0000 0.140348 3.8191 48 0.0000 0.158249 4.3062 49 0.0000 0.167569 4.5598 50 0.0000 0.175813 4.7841 *Only the first 10 virtual orbitals were printed. ******************************** * MULLIKEN POPULATION ANALYSIS * ******************************** ----------------------- MULLIKEN ATOMIC CHARGES ----------------------- 0 C : -0.170790 1 C : -0.123751 2 C : -0.104041 3 H : 0.201095 4 H : 0.174714 5 C : -0.000660 6 C : 0.007538 7 Cl: -0.068348 8 C : -0.072037 9 H : 0.189204 10 H : 0.191153 11 N : 0.495156 12 O : -0.359131 13 O : -0.360102 Sum of atomic charges: -0.0000000 -------------------------------- MULLIKEN REDUCED ORBITAL CHARGES -------------------------------- 0 C s : 3.235928 s : 3.235928 pz : 1.035494 p : 2.855574 px : 0.887452 py : 0.932628 dz2 : 0.023881 d : 0.072903 dxz : 0.014272 dyz : 0.008673 dx2y2 : 0.011873 dxy : 0.014204 f0 : 0.000488 f : 0.006385 f+1 : 0.001632 f-1 : 0.000324 f+2 : 0.000878 f-2 : 0.000879 f+3 : 0.001247 f-3 : 0.000936 1 C s : 3.186820 s : 3.186820 pz : 0.891331 p : 2.850424 px : 1.026089 py : 0.933004 dz2 : 0.017103 d : 0.079784 dxz : 0.020166 dyz : 0.019758 dx2y2 : 0.010616 dxy : 0.012141 f0 : 0.000881 f : 0.006724 f+1 : 0.002058 f-1 : 0.001267 f+2 : 0.000491 f-2 : 0.000517 f+3 : 0.000709 f-3 : 0.000802 2 C s : 3.197941 s : 3.197941 pz : 0.899803 p : 2.825980 px : 1.004659 py : 0.921517 dz2 : 0.017164 d : 0.073473 dxz : 0.017480 dyz : 0.017963 dx2y2 : 0.011467 dxy : 0.009398 f0 : 0.000849 f : 0.006647 f+1 : 0.001962 f-1 : 0.001334 f+2 : 0.000559 f-2 : 0.000487 f+3 : 0.000796 f-3 : 0.000660 3 H s : 0.767593 s : 0.767593 pz : 0.008429 p : 0.030059 px : 0.012621 py : 0.009010 dz2 : 0.000295 d : 0.001253 dxz : 0.000390 dyz : 0.000124 dx2y2 : 0.000224 dxy : 0.000219 4 H s : 0.791972 s : 0.791972 pz : 0.010252 p : 0.031995 px : 0.013267 py : 0.008476 dz2 : 0.000354 d : 0.001318 dxz : 0.000407 dyz : 0.000105 dx2y2 : 0.000220 dxy : 0.000233 5 C s : 3.122187 s : 3.122187 pz : 0.924585 p : 2.780577 px : 0.836202 py : 1.019790 dz2 : 0.011135 d : 0.087570 dxz : 0.026056 dyz : 0.023878 dx2y2 : 0.013717 dxy : 0.012784 f0 : 0.000938 f : 0.010327 f+1 : 0.002894 f-1 : 0.001406 f+2 : 0.001105 f-2 : 0.000909 f+3 : 0.001625 f-3 : 0.001450 6 C s : 3.144201 s : 3.144201 pz : 0.875316 p : 2.705278 px : 0.852039 py : 0.977923 dz2 : 0.025797 d : 0.133376 dxz : 0.035425 dyz : 0.026467 dx2y2 : 0.021793 dxy : 0.023893 f0 : 0.000866 f : 0.009607 f+1 : 0.002609 f-1 : 0.001397 f+2 : 0.000947 f-2 : 0.001011 f+3 : 0.001478 f-3 : 0.001299 7 Cls : 5.879558 s : 5.879558 pz : 3.789505 p : 11.124128 px : 3.491755 py : 3.842868 dz2 : 0.006092 d : 0.058956 dxz : 0.017738 dyz : 0.006578 dx2y2 : 0.013878 dxy : 0.014670 f0 : 0.000674 f : 0.005705 f+1 : 0.000811 f-1 : 0.000158 f+2 : 0.001135 f-2 : 0.001145 f+3 : 0.000828 f-3 : 0.000955 8 C s : 3.116753 s : 3.116753 pz : 1.060718 p : 2.871209 px : 0.893526 py : 0.916965 dz2 : 0.016163 d : 0.077032 dxz : 0.016969 dyz : 0.009265 dx2y2 : 0.016420 dxy : 0.018216 f0 : 0.000567 f : 0.007042 f+1 : 0.001628 f-1 : 0.000335 f+2 : 0.000967 f-2 : 0.000982 f+3 : 0.001351 f-3 : 0.001211 9 H s : 0.776141 s : 0.776141 pz : 0.018383 p : 0.033250 px : 0.006823 py : 0.008043 dz2 : 0.000422 d : 0.001405 dxz : 0.000614 dyz : 0.000326 dx2y2 : 0.000024 dxy : 0.000020 10 H s : 0.778504 s : 0.778504 pz : 0.015300 p : 0.029189 px : 0.005689 py : 0.008200 dz2 : 0.000351 d : 0.001155 dxz : 0.000447 dyz : 0.000314 dx2y2 : 0.000022 dxy : 0.000020 11 N s : 3.233830 s : 3.233830 pz : 0.899742 p : 2.996837 px : 1.036540 py : 1.060555 dz2 : 0.060451 d : 0.259527 dxz : 0.081857 dyz : 0.062866 dx2y2 : 0.027955 dxy : 0.026399 f0 : 0.001860 f : 0.014650 f+1 : 0.005183 f-1 : 0.002633 f+2 : 0.001169 f-2 : 0.001252 f+3 : 0.001363 f-3 : 0.001189 12 O s : 3.910273 s : 3.910273 pz : 1.639366 p : 4.403031 px : 1.364947 py : 1.398718 dz2 : 0.005508 d : 0.042283 dxz : 0.012482 dyz : 0.004972 dx2y2 : 0.009374 dxy : 0.009947 f0 : 0.000424 f : 0.003545 f+1 : 0.000660 f-1 : 0.000126 f+2 : 0.000734 f-2 : 0.000762 f+3 : 0.000437 f-3 : 0.000401 13 O s : 3.909786 s : 3.909786 pz : 1.124278 p : 4.404434 px : 1.805955 py : 1.474201 dz2 : 0.019838 d : 0.042335 dxz : 0.008819 dyz : 0.012980 dx2y2 : 0.000341 dxy : 0.000357 f0 : 0.001610 f : 0.003546 f+1 : 0.000816 f-1 : 0.001018 f+2 : 0.000044 f-2 : 0.000039 f+3 : 0.000010 f-3 : 0.000010 ******************************* * LOEWDIN POPULATION ANALYSIS * ******************************* ---------------------- LOEWDIN ATOMIC CHARGES ---------------------- 0 C : 0.013499 1 C : 0.026855 2 C : -0.000662 3 H : 0.035296 4 H : 0.036676 5 C : -0.123908 6 C : -0.400264 7 Cl: 0.414807 8 C : 0.001538 9 H : 0.035445 10 H : 0.038694 11 N : -0.021393 12 O : -0.028195 13 O : -0.028388 ------------------------------- LOEWDIN REDUCED ORBITAL CHARGES ------------------------------- 0 C s : 2.718153 s : 2.718153 pz : 0.991612 p : 2.838120 px : 0.994681 py : 0.851827 dz2 : 0.119398 d : 0.387011 dxz : 0.098677 dyz : 0.029166 dx2y2 : 0.069561 dxy : 0.070209 f0 : 0.004295 f : 0.043217 f+1 : 0.013479 f-1 : 0.002125 f+2 : 0.006771 f-2 : 0.006883 f+3 : 0.004501 f-3 : 0.005162 1 C s : 2.717354 s : 2.717354 pz : 0.994670 p : 2.825322 px : 0.993516 py : 0.837136 dz2 : 0.110602 d : 0.386225 dxz : 0.120811 dyz : 0.072731 dx2y2 : 0.039559 dxy : 0.042521 f0 : 0.007879 f : 0.044245 f+1 : 0.014365 f-1 : 0.007313 f+2 : 0.004130 f-2 : 0.003784 f+3 : 0.002917 f-3 : 0.003858 2 C s : 2.724655 s : 2.724655 pz : 1.009031 p : 2.840470 px : 0.991338 py : 0.840100 dz2 : 0.109585 d : 0.391834 dxz : 0.128829 dyz : 0.072606 dx2y2 : 0.044560 dxy : 0.036254 f0 : 0.007731 f : 0.043703 f+1 : 0.013790 f-1 : 0.007606 f+2 : 0.003898 f-2 : 0.003971 f+3 : 0.003289 f-3 : 0.003418 3 H s : 0.782895 s : 0.782895 pz : 0.043836 p : 0.152358 px : 0.066518 py : 0.042004 dz2 : 0.005253 d : 0.029451 dxz : 0.008300 dyz : 0.002940 dx2y2 : 0.006502 dxy : 0.006456 4 H s : 0.787742 s : 0.787742 pz : 0.043492 p : 0.146481 px : 0.063992 py : 0.038996 dz2 : 0.005464 d : 0.029101 dxz : 0.008452 dyz : 0.002567 dx2y2 : 0.006340 dxy : 0.006279 5 C s : 2.709484 s : 2.709484 pz : 1.007318 p : 2.816357 px : 0.888288 py : 0.920752 dz2 : 0.121553 d : 0.531523 dxz : 0.180539 dyz : 0.089968 dx2y2 : 0.075000 dxy : 0.064463 f0 : 0.008465 f : 0.066544 f+1 : 0.020533 f-1 : 0.007563 f+2 : 0.008329 f-2 : 0.007622 f+3 : 0.006976 f-3 : 0.007055 6 C s : 2.770819 s : 2.770819 pz : 1.057513 p : 2.956995 px : 0.980316 py : 0.919166 dz2 : 0.140473 d : 0.608914 dxz : 0.194070 dyz : 0.094279 dx2y2 : 0.088073 dxy : 0.092020 f0 : 0.007585 f : 0.063536 f+1 : 0.021456 f-1 : 0.007450 f+2 : 0.007211 f-2 : 0.007238 f+3 : 0.006122 f-3 : 0.006475 7 Cls : 5.528967 s : 5.528967 pz : 3.706389 p : 10.941444 px : 3.462395 py : 3.772660 dz2 : 0.012964 d : 0.102511 dxz : 0.029912 dyz : 0.011197 dx2y2 : 0.023760 dxy : 0.024678 f0 : 0.001205 f : 0.012272 f+1 : 0.002314 f-1 : 0.000425 f+2 : 0.002268 f-2 : 0.002294 f+3 : 0.001868 f-3 : 0.001898 8 C s : 2.720335 s : 2.720335 pz : 1.003225 p : 2.845882 px : 0.995181 py : 0.847475 dz2 : 0.105268 d : 0.387179 dxz : 0.102688 dyz : 0.030907 dx2y2 : 0.072293 dxy : 0.076023 f0 : 0.004516 f : 0.045067 f+1 : 0.011980 f-1 : 0.001925 f+2 : 0.007826 f-2 : 0.008009 f+3 : 0.005135 f-3 : 0.005676 9 H s : 0.781643 s : 0.781643 pz : 0.079922 p : 0.153119 px : 0.036002 py : 0.037195 dz2 : 0.011682 d : 0.029793 dxz : 0.009245 dyz : 0.008438 dx2y2 : 0.000233 dxy : 0.000195 10 H s : 0.785986 s : 0.785986 pz : 0.075567 p : 0.146438 px : 0.033396 py : 0.037475 dz2 : 0.011288 d : 0.028882 dxz : 0.009118 dyz : 0.008239 dx2y2 : 0.000118 dxy : 0.000119 11 N s : 2.911642 s : 2.911642 pz : 1.117114 p : 3.244784 px : 1.123517 py : 1.004153 dz2 : 0.207711 d : 0.788748 dxz : 0.255308 dyz : 0.161421 dx2y2 : 0.084542 dxy : 0.079766 f0 : 0.010337 f : 0.076219 f+1 : 0.030163 f-1 : 0.012373 f+2 : 0.005719 f-2 : 0.007015 f+3 : 0.005305 f-3 : 0.005308 12 O s : 3.484797 s : 3.484797 pz : 1.617636 p : 4.430590 px : 1.435753 py : 1.377200 dz2 : 0.015351 d : 0.101257 dxz : 0.032054 dyz : 0.011489 dx2y2 : 0.020881 dxy : 0.021482 f0 : 0.001293 f : 0.011551 f+1 : 0.002335 f-1 : 0.000484 f+2 : 0.002227 f-2 : 0.002345 f+3 : 0.001292 f-3 : 0.001576 13 O s : 3.484340 s : 3.484340 pz : 1.309639 p : 4.431075 px : 1.699059 py : 1.422377 dz2 : 0.052719 d : 0.101403 dxz : 0.023314 dyz : 0.024072 dx2y2 : 0.000648 dxy : 0.000651 f0 : 0.005503 f : 0.011571 f+1 : 0.002979 f-1 : 0.002836 f+2 : 0.000111 f-2 : 0.000118 f+3 : 0.000010 f-3 : 0.000014 ***************************** * 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 6.1708 6.0000 -0.1708 3.9772 3.9772 0.0000 1 C 6.1238 6.0000 -0.1238 3.9795 3.9795 0.0000 2 C 6.1040 6.0000 -0.1040 3.9372 3.9372 -0.0000 3 H 0.7989 1.0000 0.2011 0.9889 0.9889 0.0000 4 H 0.8253 1.0000 0.1747 0.9866 0.9866 -0.0000 5 C 6.0007 6.0000 -0.0007 3.9295 3.9295 -0.0000 6 C 5.9925 6.0000 0.0075 3.9998 3.9998 -0.0000 7 Cl 17.0683 17.0000 -0.0683 1.2278 1.2278 -0.0000 8 C 6.0720 6.0000 -0.0720 3.9816 3.9816 -0.0000 9 H 0.8108 1.0000 0.1892 1.0004 1.0004 -0.0000 10 H 0.8088 1.0000 0.1912 0.9761 0.9761 0.0000 11 N 6.5048 7.0000 0.4952 4.1185 4.1185 -0.0000 12 O 8.3591 8.0000 -0.3591 1.8334 1.8334 -0.0000 13 O 8.3601 8.0000 -0.3601 1.8355 1.8355 0.0000 Mayer bond orders larger than 0.100000 B( 0-C , 1-C ) : 1.4710 B( 0-C , 2-C ) : 1.4401 B( 0-C , 10-H ) : 0.9472 B( 1-C , 3-H ) : 0.9039 B( 1-C , 5-C ) : 1.4058 B( 2-C , 4-H ) : 0.9432 B( 2-C , 6-C ) : 1.3789 B( 5-C , 8-C ) : 1.4350 B( 5-C , 11-N ) : 0.9650 B( 6-C , 7-Cl) : 1.0759 B( 6-C , 8-C ) : 1.4353 B( 8-C , 9-H ) : 0.8798 B( 11-N , 12-O ) : 1.5702 B( 11-N , 13-O ) : 1.5722 B( 12-O , 13-O ) : 0.1657 ------- TIMINGS ------- Total SCF time: 0 days 0 hours 0 min 42 sec Total time .... 42.906 sec Sum of individual times .... 42.917 sec (100.0%) SCF preparation .... 0.389 sec ( 0.9%) Fock matrix formation .... 41.749 sec ( 97.3%) Startup .... 0.019 sec ( 0.0% of F) Split-RI-J .... 2.212 sec ( 5.3% of F) Chain of spheres X .... 27.655 sec ( 66.2% of F) XC integration .... 9.133 sec ( 21.9% of F) XC Preparation .... 0.000 sec ( 0.0% of XC) Basis function eval. .... 1.086 sec ( 11.9% of XC) Density eval. .... 2.511 sec ( 27.5% of XC) XC-Functional eval. .... 0.218 sec ( 2.4% of XC) XC-Potential eval. .... 4.086 sec ( 44.7% of XC) CPCM terms .... 2.660 sec ( 6.4% of F) Diagonalization .... 0.000 sec ( 0.0%) Density matrix formation .... 0.054 sec ( 0.1%) Total Energy calculation .... 0.040 sec ( 0.1%) Population analysis .... 0.039 sec ( 0.1%) Orbital Transformation .... 0.088 sec ( 0.2%) Orbital Orthonormalization .... 0.000 sec ( 0.0%) DIIS solution .... 0.402 sec ( 0.9%) SOSCF solution .... 0.149 sec ( 0.3%) Finished LeanSCF after 43.0 sec Maximum memory used throughout the entire LEANSCF-calculation: 39.2 MB ************************************************************ * Program running with 4 parallel MPI-processes * * working on a common directory * ************************************************************ ------------------------------------------------------------------------------ ORCA PROPERTY INTEGRAL CALCULATIONS ------------------------------------------------------------------------------ GBWName ... nitrochlorobenz.gbw Number of atoms ... 14 Number of basis functions ... 377 Max core memory ... 3000 MB Dipole integrals ... YES Quadrupole integrals ... NO Linear momentum integrals ... YES Angular momentum integrals ... YES Higher moments length integrals ... NO Higher moments velocity integrals ... NO Kinetic energy integrals ... NO GIAO right hand sides ... NO GIAO dipole derivative integrals ... NO SOC integrals ... NO EPR diamagnetic integrals (GIAO) ... NO EPR gauge integrals ... NO Field gradient integrals ... NO ( 0 nuclei) Spin-dipole/Fermi contact integrals ... NO ( 0 nuclei) Contact density integrals ... NO ( 0 nuclei) Nucleus-orbit integrals ... NO ( 0 nuclei) Geometric perturbations ... NO ( 14 nuclei) Choice of electric origin ... Center of mass Position of electric origin ... ( 0.1287, 0.1570, 0.0739) Choice of magnetic origin ... GIAO Position of magnetic origin ... ( 0.0000, 0.0000, 0.0000) Calculating integrals ... Electric Dipole (Length) done ( 0.0 sec) Calculating integrals ... Linear Momentum done ( 0.0 sec) Calculating integrals ... Angular Momentum (ElOri) done ( 0.0 sec) Property integrals calculated in 0.1 sec Maximum memory used throughout the entire PROPINT-calculation: 25.1 MB ************************************************************ * Program running with 4 parallel MPI-processes * * working on a common directory * ************************************************************ ------------------------------------------------------------------------------ ORCA TD-DFT/TDA CALCULATION ------------------------------------------------------------------------------ Input orbitals are from ... nitrochlorobenz.gbw CI-vector output ... nitrochlorobenz.cis Solver ... FN-2001 Tamm-Dancoff approximation ... operative CIS-Integral strategy ... AO-integrals Integral handling ... AO integral Direct Max. core memory used ... 3000 MB Reference state ... RHF Generation of triplets ... off Follow IRoot ... off Number of operators ... 1 Orbital ranges used for CIS calculation: Operator 0: Orbitals 14... 39 to 40...376 XAS localization array: Operator 0: Orbitals -1... -1 ------------------- XC-INTEGRATION GRID ------------------- General Integration Accuracy IntAcc ... 3.467 Radial Grid Type RadialGrid ... OptM3 with GC (2021) Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) Angular grid pruning method GridPruning ... 4 (adaptive) Weight generation scheme WeightScheme... mBecke (2022) Basis function cutoff BFCut ... 1.0000e-10 Integration weight cutoff WCut ... 1.0000e-14 Partially contracted basis set ... off Rotationally invariant grid construction ... off Angular grids for H and He will be reduced by one unit Total number of grid points ... 12041 Total number of batches ... 193 Average number of points per batch ... 62 Average number of grid points per atom ... 860 --------------------- COSX-INTEGRATION GRID --------------------- General Integration Accuracy IntAcc ... 3.067 Radial Grid Type RadialGrid ... OptM3 with GC (2021) Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) Angular grid pruning method GridPruning ... 4 (adaptive) Weight generation scheme WeightScheme... mBecke (2022) Basis function cutoff BFCut ... 1.0000e-10 Integration weight cutoff WCut ... 1.0000e-14 Partially contracted basis set ... on Rotationally invariant grid construction ... off Angular grids for H and He will be reduced by one unit Total number of grid points ... 5851 Total number of batches ... 53 Average number of points per batch ... 110 Average number of grid points per atom ... 418 --------------- TD-DFT XC SETUP --------------- DFT calculation ... on Name of the grid file ... nitrochlorobenz.grid_cis.tmp RI-approximation ... on Aux-basis dimension ... 0 Exchange functional (TD-DFT) ... M062X Correlation functional (TD-DFT) ... M062X Hybrid DFT ... on Exchange mixing (TD-DFT) ... 0.540 GGA exch. scaling (TD-DFT) ... 0.460 GGA corr. scaling (TD-DFT) ... 1.000 Building densities ... done Calculating rho(r) on the grid ... done Building xc-kernel on the grid ... done *** TD-DFT CALCULATION INITIALIZED *** --------------------------------- LR-CPCM (non-equilibrium) --------------------------------- Setting up LR-CPCM ... done ------------------------ DAVIDSON-DIAGONALIZATION ------------------------ Dimension of the eigenvalue problem ... 8762 Number of roots to be determined ... 3 Maximum size of the expansion space ... 30 Maximum number of iterations ... 100 Convergence tolerance for the residual ... 1.000e-06 Convergence tolerance for the energies ... 1.000e-06 Orthogonality tolerance ... 1.000e-14 Level Shift ... 0.000e+00 Constructing the preconditioner ... o.k. Building the initial guess ... o.k. Number of trial vectors determined ... 30 ****Iteration 0**** Time for iteration : TOTAL=5.9 TRAFO=0.0 RIJ=0.6 COSX=2.0 XC=1.8 Size of expansion space: 9 Lowest Energy : 0.177657473502 Maximum Energy change : 0.194198838619 (vector 2) Maximum residual norm : 0.006489377259 ****Iteration 1**** Time for iteration : TOTAL=3.2 TRAFO=0.0 RIJ=0.4 COSX=1.3 XC=0.6 Size of expansion space: 12 Lowest Energy : 0.154896431042 Maximum Energy change : 0.022761042460 (vector 0) Maximum residual norm : 0.001070084260 ****Iteration 2**** Time for iteration : TOTAL=3.2 TRAFO=0.0 RIJ=0.4 COSX=1.3 XC=0.7 Size of expansion space: 15 Lowest Energy : 0.154417718269 Maximum Energy change : 0.001337284118 (vector 2) Maximum residual norm : 0.000094222639 ****Iteration 3**** Time for iteration : TOTAL=3.2 TRAFO=0.0 RIJ=0.4 COSX=1.3 XC=0.7 Size of expansion space: 18 Lowest Energy : 0.154408290374 Maximum Energy change : 0.000107492993 (vector 2) Maximum residual norm : 0.000007791698 ****Iteration 4**** Time for iteration : TOTAL=3.2 TRAFO=0.0 RIJ=0.4 COSX=1.3 XC=0.7 Size of expansion space: 21 Lowest Energy : 0.154407841068 Maximum Energy change : 0.000008627182 (vector 1) Maximum residual norm : 0.000000867571 *** CONVERGENCE OF RESIDUAL NORM REACHED *** Storing the converged CI vectors ... nitrochlorobenz.cis1 *** DAVIDSON DONE *** Total time for solving the CIS problem: 18.662sec ------------------------------------ TD-DFT/TDA EXCITED STATES (SINGLETS) ------------------------------------ the weight of the individual excitations are printed if larger than 1.0e-02 STATE 1: E= 0.154408 au 4.202 eV 33888.6 cm**-1 = 0.000000 Mult 1 34a -> 40a : 0.010805 (c= -0.10394883) 36a -> 40a : 0.750977 (c= 0.86658950) 36a -> 42a : 0.105627 (c= -0.32500240) 37a -> 40a : 0.104356 (c= -0.32304133) 37a -> 42a : 0.012428 (c= 0.11148297) STATE 2: E= 0.171185 au 4.658 eV 37570.8 cm**-1 = 0.000000 Mult 1 38a -> 40a : 0.032657 (c= 0.18071129) 38a -> 41a : 0.074589 (c= 0.27310997) 39a -> 40a : 0.855834 (c= 0.92511323) 39a -> 41a : 0.013355 (c= -0.11556208) STATE 3: E= 0.171357 au 4.663 eV 37608.5 cm**-1 = 0.000000 Mult 1 31a -> 40a : 0.011679 (c= -0.10806837) 34a -> 40a : 0.699709 (c= -0.83648591) 34a -> 42a : 0.090453 (c= 0.30075427) 36a -> 40a : 0.049730 (c= -0.22300315) 37a -> 40a : 0.113650 (c= -0.33712076) ----------------------------- TD-DFT/TDA-EXCITATION SPECTRA ----------------------------- Center of mass = ( 0.1287, 0.1570, 0.0739) Generating CIS transition densities ... done ---------------------------------------------------------------------------------------------------- ABSORPTION SPECTRUM VIA TRANSITION ELECTRIC DIPOLE MOMENTS ---------------------------------------------------------------------------------------------------- Transition Energy Energy Wavelength fosc(D2) D2 DX DY DZ (eV) (cm-1) (nm) (au**2) (au) (au) (au) ---------------------------------------------------------------------------------------------------- 0-1A -> 1-1A 4.201651 33888.6 295.1 0.000000079 0.00000 -0.00038 -0.00066 -0.00043 0-1A -> 2-1A 4.658184 37570.8 266.2 0.056597499 0.49593 0.05435 -0.05249 -0.70016 0-1A -> 3-1A 4.662853 37608.5 265.9 0.000253859 0.00222 -0.00836 0.03071 -0.03477 ---------------------------------------------------------------------------------------------------- ABSORPTION SPECTRUM VIA TRANSITION VELOCITY DIPOLE MOMENTS ---------------------------------------------------------------------------------------------------- Transition Energy Energy Wavelength fosc(P2) P2 PX PY PZ (eV) (cm-1) (nm) (au**2) (au) (au) (au) ---------------------------------------------------------------------------------------------------- 0-1A -> 1-1A 4.201651 33888.6 295.1 0.000003973 0.00000 -0.00009 -0.00087 -0.00040 0-1A -> 2-1A 4.658184 37570.8 266.2 0.000790444 0.00020 -0.00825 -0.00103 0.01157 0-1A -> 3-1A 4.662853 37608.5 265.9 0.001796263 0.00046 0.00729 -0.02005 0.00259 ------------------------------------------------------------------------------------------ CD SPECTRUM VIA TRANSITION ELECTRIC DIPOLE MOMENTS ------------------------------------------------------------------------------------------ Transition Energy Energy Wavelength R MX MY MZ (eV) (cm-1) (nm) (1e40*cgs) (au) (au) (au) ------------------------------------------------------------------------------------------ 0-1A -> 1-1A 4.201651 33888.6 295.1 0.03970 0.25020 0.07566 -0.14341 0-1A -> 2-1A 4.658184 37570.8 266.2 -6.78200 -0.00829 -0.01063 -0.02039 0-1A -> 3-1A 4.662853 37608.5 265.9 6.90634 0.23491 0.13526 0.48421 ------------------------------------------------------------------------------------------ CD SPECTRUM VIA TRANSITION VELOCITY DIPOLE MOMENTS ------------------------------------------------------------------------------------------ Transition Energy Energy Wavelength R MX MY MZ (eV) (cm-1) (nm) (1e40*cgs) (au) (au) (au) ------------------------------------------------------------------------------------------ 0-1A -> 1-1A 4.201651 33888.6 295.1 -0.09331 0.25020 0.07566 -0.14341 0-1A -> 2-1A 4.658184 37570.8 266.2 -0.43124 -0.00829 -0.01063 -0.02039 0-1A -> 3-1A 4.662853 37608.5 265.9 0.69762 0.23491 0.13526 0.48421 Total run time: 19.109 sec *** ORCA-CIS/TD-DFT FINISHED WITHOUT ERROR *** ----------------------- CIS/TD-DFT TOTAL ENERGY ----------------------- E(SCF) = -896.356325130 Eh DE(CIS) = 0.154407841 Eh (Root 1) ----------------------------- --------- E(tot) = -896.201917289 Eh Maximum memory used throughout the entire CIS-calculation: 76.8 MB => NOW LEAVING ORCA_CIS ------------------------- -------------------- FINAL SINGLE POINT ENERGY -896.201917289392 ------------------------- -------------------- ************************************************************ * Program running with 4 parallel MPI-processes * * working on a common directory * ************************************************************ ------------------------------------------------------------------------------ ORCA PROPERTY CALCULATIONS ------------------------------------------------------------------------------ GBWName ... nitrochlorobenz.gbw Number of atoms ... 14 Number of basis functions ... 377 Max core memory ... 3000 MB Electric properties: Dipole moment ... YES Quadrupole moment ... NO Static polarizability (Dipole/Dipole) ... NO Static polarizability (Dipole/Quad.) ... NO Static polarizability (Quad./Quad.) ... NO Static polarizability (Velocity) ... NO Atomic electric properties: Dipole moment ... NO Quadrupole moment ... NO Static polarizability ... NO Choice of electric origin ... Center of mass Position of electric origin ... 0.128655 0.157011 0.073882 General magnetic properties: Magnetizability ... NO EPR properties: g-Tensor (aka g-matrix) ... NO Zero-Field splitting spin-orbit ... NO Zero-field splitting spin-spin ... NO Hyperfine couplings ... NO ( 0 nuclei) Quadrupole couplings ... NO ( 0 nuclei) Contact density ... NO ( 0 nuclei) NMR properties: Chemical shifts ... NO ( 0 nuclei) Spin-rotation constants ... NO ( 0 nuclei) Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) Choice of magnetic origin ... GIAO Position of magnetic origin ... 0.000000 0.000000 0.000000 Properties with geometric perturbations: SCF Hessian ... NO IR spectrum ... NO VCD spectrum ... NO X-ray spectroscopy properties: SCF XES/XAS/RIXS spectra ... NO ------------- DIPOLE MOMENT ------------- Method : SCF Type of density : Electron Density Multiplicity : 1 Irrep : 0 Energy : -896.3563251304597088 Eh Relativity type : Basis : AO X Y Z Electronic contribution: 4.091628714 1.958211310 4.638397023 Nuclear contribution : -2.876913917 -1.675551334 -6.224881042 ----------------------------------------- Total Dipole Moment : 1.214714797 0.282659976 -1.586484019 ----------------------------------------- Magnitude (a.u.) : 2.018008980 Magnitude (Debye) : 5.129371188 -------------------- Rotational spectrum -------------------- Rotational constants in cm-1: 0.078134 0.024274 0.018521 Rotational constants in MHz : 2342.407061 727.727856 555.231355 Dipole components along the rotational axes: x,y,z [a.u.] : 1.300227 1.543298 0.000152 x,y,z [Debye]: 3.304915 3.922752 0.000386 Dipole moment calculation done in 0.0 sec Maximum memory used throughout the entire PROP-calculation: 22.0 MB -------------------------------- SUGGESTED CITATIONS FOR THIS RUN -------------------------------- Below you find a list of papers that are relevant to this ORCA run We neither can nor want to force you to cite these papers, but we appreciate if you do You receive ORCA, which is the product of decades of hard work by many enthusiastic individuals, for free The only thing we kindly ask in return is that you cite our papers, We deeply appreciate it, if you show your appreciation for ORCA by not just citing the generic ORCA reference. Please note that relegating all ORCA citations to the supporting information does *not* help us. SI sections are not indexed - citations you put there will not count into any citation statistics But we need these citations in order to attract the funding resources that allow us to do what we are doing Therefore, if you are a happy ORCA user, please consider citing a few of the papers listed below in the main body of your paper In addition to the list printed below, the program has created the file nitrochlorobenz.bibtex that contains the list in bibtex format You can import this file easily into all common literature databanks and citation aid programs List of essential papers. We consider these as the minimum necessary citations 1. Neese,F. Software update: the ORCA program system, version 5.0 WIRES Comput. Molec. Sci., 2022 12(1)e1606 doi.org/10.1002/wcms.1606 List of papers to cite with high priority. The work reported in these papers was absolutely necessary for this run to complete. Our perspective: the developers of density functionals and basis sets usually get cited in chemistry papers Good! But without the algorithms to do something with them, the functionals or basis sets would not do anything. Hence, in our opinion, the algorithm design and method developments papers are equally worthy of getting cited 1. Neese,F.; Olbrich,G. Efficient use of the resolution of the identity approximation in time-dependent density functional calculations with hybrid density functionals Chem. Phys. Lett., 2002 362 170-178 doi.org/10.1016/s0009-2614(02)01053-9 2. Neese,F. An improvement of the resolution of the identity approximation for the formation of the Coulomb matrix J. Comp. Chem., 2003 24(14)1740-1747 doi.org/10.1002/jcc.10318 3. Neese,F.; Wennmohs,F.; Hansen,A.; Becker,U. Efficient, approximate and parallel Hartree-Fock and hybrid DFT calculations. A 'chain-of-spheres' algorithm for the Hartree-Fock exchange Chem. Phys., 2009 356(1-3)98-109 doi.org/10.1016/j.chemphys.2008.10.036 4. Garcia-Rates,M.; Neese,F. Effect of the Solute Cavity on the Solvation Energy and its Derivatives within the Framework of the Gaussian Charge Scheme J. Comput. Chem., 2020 41 922-939 doi.org/10.1002/jcc.26139 5. Helmich-Paris,B.; de Souza,B.; Neese,F.; Izsák,R. An improved chain of spheres for exchange algorithm J. Chem. Phys., 2021 155 104109 doi.org/doi: 10.1063/5.0058766. 6. Neese,F. The SHARK Integral Generation and Digestion System J. Comp. Chem., 2022 1-16 doi.org/10.1002/jcc.26942 List of suggested additional citations. These are papers that are important in the 'surrounding' of of this run, or papers that preceded the highly important papers. If you like your results we are grateful for a citation. 1. Izsak,R.; Neese,F. An overlap fitted chain of spheres exchange method J. Chem. Phys., 2011 135 144105 doi.org/10.1063/1.3646921 2. Izsak,R.; Hansen,A.; Neese,F. The resolution of identity and chain of spheres approximations for the LPNO-CCSD singles Fock term Molec. Phys., 2012 110 2413-2417 doi.org/10.1080/00268976.2012.687466 3. Neese,F. The ORCA program system WIRES Comput. Molec. Sci., 2012 2(1)73-78 doi.org/10.1002/wcms.81 4. Izsak,R.; Neese,F.; Klopper,W. Robust fitting techniques in the chain of spheres approximation to the Fock exchange: The role of the complementary space J. Chem. Phys., 2013 139 doi.org/10.1063/1.4819264 5. Neese,F. Software update: the ORCA program system, version 4.0 WIRES Comput. Molec. Sci., 2018 8(1)1-6 doi.org/10.1002/wcms.1327 6. Neese,F.; Wennmohs,F.; Becker,U.; Riplinger,C. The ORCA quantum chemistry program package J. Chem. Phys., 2020 152 Art. No. L224108 doi.org/10.1063/5.0004608 List of optional additional citations 1. Neese,F. Approximate second-order SCF convergence for spin unrestricted wavefunctions Chem. Phys. Lett., 2000 325(1-3)93-98 doi.org/10.1016/s0009-2614(00)00662-x Timings for individual modules: Sum of individual times ... 66.405 sec (= 1.107 min) Startup calculation ... 1.844 sec (= 0.031 min) 2.8 % SCF iterations ... 44.090 sec (= 0.735 min) 66.4 % Property integrals ... 0.526 sec (= 0.009 min) 0.8 % Property calculations ... 0.425 sec (= 0.007 min) 0.6 % CIS module ... 19.520 sec (= 0.325 min) 29.4 % ****ORCA TERMINATED NORMALLY**** TOTAL RUN TIME: 0 days 0 hours 1 minutes 6 seconds 843 msec