nohup: ignoring input ***************** * 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 6.1.0 - RELEASE - (GIT: $679e74b$) ($2025-06-10 18:02:51 +0200$) 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 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., MC-PDFT, srDFT 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, approximate NEVPT4 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, Hyperfine gauge corrections, ICE-SOC+SSC 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, Property file 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, ECA, NRVS Petra Pikulova : Analytic Raman intensities Peter Pinski : DLPNO-MP2, DLPNO-MP2 Gradient Shashank Vittal Rao : ES-AILFT, MagRelax 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, recursive CI coupling coefficients Masaaki Saitow : Open-shell DLPNO-CCSD energy and density Barbara Sandhoefer : DKH picture change effects Yorick L. A. Schmerwitz: GMF and freeze-and-release deltaSCF, NEB S-IDPP initial path Kantharuban Sivalingam : CASSCF convergence/infrastructure, NEVPT2, NEVPT3, NEVPT4(SD), FIC-MRCI and CEPA variants 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, Nicolas Foglia, Miquel Garcia-Rates, Ingolf Harden, Hagen Neugebauer, Anastasios Papadopoulos, Christoph Riplinger, Bernardo de Souza, Georgi L. Stoychev APM, various basis sets, CI-OPT, improved COSX, DLPNO-Multilevel, DOCKER, DRACO, updates on ESD, Fragmentator, GOAT, IRC, LR-CPCM, L-BFGS, 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, RESP, rigid body optimization, SF, symmetry and pop. for TD-DFT, various functionals, SOLVATOR [Other institutions] V. Asgeirsson : NEB Christoph Bannwarth : sTDA-DFT, sTD-DFT, PBEh-3c, B97-3c, D3 Giovanni Bistoni : ETS/NOCV, ADLD/ADEX, COVALED Martin Brehm : Molecular dynamics Ronald Cardenas : ETS/NOCV Martina Colucci : COVALED 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, Native XTB Gianluca Regni : ADLD/ADEX Tobias Risthaus : pre 6.0 range-separated hybrid DFT and stability analysis 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: 7.0.0 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 0.3.29 USE64BITINT DYNAMIC_ARCH NO_AFFINITY SkylakeX SINGLE_THREADED Core in use : SkylakeX Copyright (c) 2011-2014, The OpenBLAS Project *********************************** * Starting time: Tue Jul 7 12:42:43 2026 * Host name: dirac.ttk.pte.hu * Process ID: 3675418 * Working dir.: /home/nora/SU/P3_tddft/caffeine *********************************** *************************************** The coordinates will be read from file: caffeine_opt.xyz *************************************** 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-TZVP F. Weigend and R. Ahlrichs, Phys. Chem. Chem. Phys. 7, 3297 (2005). ----- AuxJ basis set information ----- Your calculation utilizes the auxiliary basis: def2/J H-Rn: F. Weigend, Phys. Chem. Chem. Phys. 8, 1057 (2006). Fr-Lr: K. Eichkorn, F. Weigend, O. Treutler, R. Ahlrichs; Theor. Chem. Acc. 97, 119 (1997). ================================================================================ WARNINGS Please study these warnings very carefully! ================================================================================ WARNING: Old DensityContainer found on disk! Will remove this file - If you want to keep old densities, please start your calculation with a different basename. WARNING: CIS/ROCIS methods need fully converged wavefunctions ===> : Setting SCFConvForced true You can overwrite this default with %scf ConvForced false ================================================================================ INPUT FILE ================================================================================ NAME = caffeine_tddft.inp | 1> ! B3LYP def2-TZVP TightSCF FIC-NEVPT2 | 2> | 3> %pal | 4> nprocs 30 | 5> end | 6> | 7> %tddft | 8> nroots 10 | 9> end | 10> | 11> * xyzfile 0 1 caffeine_opt.xyz | 12> | 13> | 14> ****END OF INPUT**** ================================================================================ **************************** * Single Point Calculation * **************************** --------------------------------- CARTESIAN COORDINATES (ANGSTROEM) --------------------------------- N 1.533599 0.650219 -0.057445 C 1.688747 -0.742527 -0.139326 N 0.538345 -1.515150 -0.084756 C 0.316651 1.357179 0.076798 C -0.799471 0.465104 0.122694 C -0.683169 -0.905533 0.045175 N -2.157644 0.707533 0.245773 C -2.748536 -0.506736 0.233701 N -1.892664 -1.512311 0.114024 C 0.674429 -2.966761 -0.168600 O 2.788496 -1.250227 -0.253585 O 0.270834 2.576657 0.141739 C -2.810101 2.002649 0.361687 C 2.776660 1.422297 -0.118189 H -3.818552 -0.618644 0.315606 H 1.152830 -3.244954 -1.106966 H -0.320839 -3.397560 -0.113038 H 1.289167 -3.334426 0.652291 H -2.600140 2.612267 -0.515671 H -2.448082 2.531029 1.242015 H -3.882972 1.839305 0.446712 H 3.291688 1.228994 -1.058253 H 3.436466 1.132736 0.698437 H 2.512857 2.471562 -0.039522 ---------------------------- CARTESIAN COORDINATES (A.U.) ---------------------------- NO LB ZA FRAG MASS X Y Z 0 N 7.0000 0 14.007 2.898083 1.228736 -0.108555 1 C 6.0000 0 12.011 3.191269 -1.403172 -0.263288 2 N 7.0000 0 14.007 1.017326 -2.863219 -0.160166 3 C 6.0000 0 12.011 0.598384 2.564696 0.145126 4 C 6.0000 0 12.011 -1.510782 0.878919 0.231858 5 C 6.0000 0 12.011 -1.291002 -1.711209 0.085368 6 N 7.0000 0 14.007 -4.077355 1.337043 0.464443 7 C 6.0000 0 12.011 -5.193980 -0.957593 0.441631 8 N 7.0000 0 14.007 -3.576617 -2.857854 0.215475 9 C 6.0000 0 12.011 1.274486 -5.606366 -0.318608 10 O 8.0000 0 15.999 5.269494 -2.362587 -0.479207 11 O 8.0000 0 15.999 0.511802 4.869176 0.267848 12 C 6.0000 0 12.011 -5.310321 3.784459 0.683489 13 C 6.0000 0 12.011 5.247126 2.687751 -0.223344 14 H 1.0000 0 1.008 -7.216017 -1.169068 0.596408 15 H 1.0000 0 1.008 2.178533 -6.132075 -2.091862 16 H 1.0000 0 1.008 -0.606298 -6.420459 -0.213610 17 H 1.0000 0 1.008 2.436172 -6.301152 1.232651 18 H 1.0000 0 1.008 -4.913552 4.936470 -0.974477 19 H 1.0000 0 1.008 -4.626205 4.782952 2.347068 20 H 1.0000 0 1.008 -7.337754 3.475782 0.844163 21 H 1.0000 0 1.008 6.220390 2.322462 -1.999808 22 H 1.0000 0 1.008 6.493980 2.140561 1.319854 23 H 1.0000 0 1.008 4.748612 4.670575 -0.074687 -------------------------------- INTERNAL COORDINATES (ANGSTROEM) -------------------------------- N 0 0 0 0.000000000000 0.00000000 0.00000000 C 1 0 0 1.403750777847 0.00000000 0.00000000 N 2 1 0 1.386848232786 117.30744176 0.00000000 C 1 2 3 1.413780513434 126.64127603 0.03187755 C 4 1 2 1.429556867351 111.28796048 359.97295429 C 3 2 1 1.371354302034 119.66613017 359.96175484 N 5 4 1 1.385118133367 131.23833196 179.96400011 C 7 5 4 1.350462410414 105.71598100 180.05236886 N 8 7 5 1.325903486773 113.59641469 0.00000000 C 3 2 1 1.460384219686 118.30761597 179.97452767 O 2 1 3 1.216660906541 121.29198902 179.99734448 O 4 1 2 1.222065580369 122.43266259 179.96804753 C 7 5 4 1.454807006151 127.05999410 0.14158632 C 1 2 3 1.464579101830 115.26516673 179.94200346 H 8 7 5 1.078965392798 121.76917704 180.00004545 H 10 3 2 1.089398513980 110.13316342 300.46642938 H 10 3 2 1.085925653316 107.81753732 180.19680652 H 10 3 2 1.089468456086 110.16742706 59.94643797 H 13 7 5 1.088794862919 110.34999566 60.16187480 H 13 7 5 1.088678081221 110.32590224 300.39350507 H 13 7 5 1.088560595941 108.34022247 180.27034329 H 14 1 2 1.089193086752 110.09467660 59.94694073 H 14 1 2 1.089066959896 110.05662338 300.67529492 H 14 1 2 1.084775349259 107.48753088 180.28925342 --------------------------- INTERNAL COORDINATES (A.U.) --------------------------- N 0 0 0 0.000000000000 0.00000000 0.00000000 C 1 0 0 2.652704530410 0.00000000 0.00000000 N 2 1 0 2.620763349279 117.30744176 0.00000000 C 1 2 3 2.671657983865 126.64127603 0.03187755 C 4 1 2 2.701470972160 111.28796048 359.97295429 C 3 2 1 2.591484063420 119.66613017 359.96175484 N 5 4 1 2.617493935191 131.23833196 179.96400011 C 7 5 4 2.552004109838 105.71598100 180.05236886 N 8 7 5 2.505594470013 113.59641469 0.00000000 C 3 2 1 2.759726225506 118.30761597 179.97452767 O 2 1 3 2.299155911211 121.29198902 179.99734448 O 4 1 2 2.309369264589 122.43266259 179.96804753 C 7 5 4 2.749186819336 127.05999410 0.14158632 C 1 2 3 2.767653403922 115.26516673 179.94200346 H 8 7 5 2.038949100366 121.76917704 180.00004545 H 10 3 2 2.058664842123 110.13316342 300.46642938 H 10 3 2 2.052102086567 107.81753732 180.19680652 H 10 3 2 2.058797013549 110.16742706 59.94643797 H 13 7 5 2.057524106938 110.34999566 60.16187480 H 13 7 5 2.057303421510 110.32590224 300.39350507 H 13 7 5 2.057081406506 108.34022247 180.27034329 H 14 1 2 2.058276640921 110.09467660 59.94694073 H 14 1 2 2.058038295706 110.05662338 300.67529492 H 14 1 2 2.049928326928 107.48753088 180.28925342 --------------------- BASIS SET INFORMATION --------------------- There are 4 groups of distinct atoms Group 1 Type N : 11s6p2d1f contracted to 5s3p2d1f pattern {62111/411/11/1} Group 2 Type C : 11s6p2d1f contracted to 5s3p2d1f pattern {62111/411/11/1} Group 3 Type O : 11s6p2d1f contracted to 5s3p2d1f pattern {62111/411/11/1} Group 4 Type H : 5s1p contracted to 3s1p pattern {311/1} Atom 0N basis set group => 1 Atom 1C basis set group => 2 Atom 2N basis set group => 1 Atom 3C basis set group => 2 Atom 4C basis set group => 2 Atom 5C basis set group => 2 Atom 6N basis set group => 1 Atom 7C basis set group => 2 Atom 8N basis set group => 1 Atom 9C basis set group => 2 Atom 10O basis set group => 3 Atom 11O basis set group => 3 Atom 12C basis set group => 2 Atom 13C basis set group => 2 Atom 14H basis set group => 4 Atom 15H basis set group => 4 Atom 16H basis set group => 4 Atom 17H basis set group => 4 Atom 18H basis set group => 4 Atom 19H basis set group => 4 Atom 20H basis set group => 4 Atom 21H basis set group => 4 Atom 22H basis set group => 4 Atom 23H basis set group => 4 --------------------------------- AUXILIARY/J BASIS SET INFORMATION --------------------------------- There are 4 groups of distinct atoms Group 1 Type N : 12s5p4d2f1g contracted to 6s4p3d1f1g pattern {711111/2111/211/2/1} Group 2 Type C : 12s5p4d2f1g contracted to 6s4p3d1f1g pattern {711111/2111/211/2/1} Group 3 Type O : 12s5p4d2f1g contracted to 6s4p3d1f1g pattern {711111/2111/211/2/1} Group 4 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} Atom 0N basis set group => 1 Atom 1C basis set group => 2 Atom 2N basis set group => 1 Atom 3C basis set group => 2 Atom 4C basis set group => 2 Atom 5C basis set group => 2 Atom 6N basis set group => 1 Atom 7C basis set group => 2 Atom 8N basis set group => 1 Atom 9C basis set group => 2 Atom 10O basis set group => 3 Atom 11O basis set group => 3 Atom 12C basis set group => 2 Atom 13C basis set group => 2 Atom 14H basis set group => 4 Atom 15H basis set group => 4 Atom 16H basis set group => 4 Atom 17H basis set group => 4 Atom 18H basis set group => 4 Atom 19H basis set group => 4 Atom 20H basis set group => 4 Atom 21H basis set group => 4 Atom 22H basis set group => 4 Atom 23H basis set group => 4 Checking for AutoStart: The File: caffeine_tddft.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 Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified ************************************************************ * Program running with 30 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 ... 24 Number of basis functions ... 494 Number of shells ... 194 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 ... 2.500e-11 Tcut ... 2.500e-12 Tpresel ... 2.500e-12 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 ... 796 # of shells in Aux-J ... 260 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 = 194 => SHARK Basis and OBASIS are compatible. Storing Pre-screening Shell pair information Shell pair cut-off parameter TPreSel ... 2.5e-12 Total number of shell pairs ... 18915 Shell pairs after pre-screening ... 15702 Total number of primitive shell pairs ... 58308 Primitive shell pairs kept ... 34023 la=0 lb=0: 3956 shell pairs la=1 lb=0: 4379 shell pairs la=1 lb=1: 1228 shell pairs la=2 lb=0: 2318 shell pairs la=2 lb=1: 1292 shell pairs la=2 lb=2: 363 shell pairs la=3 lb=0: 1105 shell pairs la=3 lb=1: 628 shell pairs la=3 lb=2: 343 shell pairs la=3 lb=3: 90 shell pairs Checking whether 4 symmetric matrices of dimension 494 fit in memory :Max Core in MB = 4096.00 MB in use = 22.92 MB left = 4073.08 MB needed = 3.73 Data fit in memory = YES Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 929.753742142530 Eh Diagonalization of the overlap matrix: Smallest eigenvalue ... 3.842e-05 Time for diagonalization ... 0.036 sec Threshold for overlap eigenvalues ... 1.000e-07 Number of eigenvalues below threshold ... 0 Time for construction of square roots ... 0.021 sec Total time needed ... 0.059 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-11 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 ... 116084 Total number of batches ... 1827 Average number of points per batch ... 63 Average number of grid points per atom ... 4837 -------------------- 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-11 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 ... 14812 Total number of batches ... 130 Average number of points per batch ... 113 Average number of grid points per atom ... 617 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-11 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 ... 32434 Total number of batches ... 267 Average number of points per batch ... 121 Average number of grid points per atom ... 1351 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-11 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 ... 71221 Total number of batches ... 569 Average number of points per batch ... 125 Average number of grid points per atom ... 2968 UseSFitting ... on Grids setup in 1.1 sec Initializing property integral containers ... done ( 0.0 sec) SHARK setup successfully completed in 1.4 seconds Maximum memory used throughout the entire STARTUP-calculation: 43.2 MB Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified ************************************************************ * Program running with 30 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 .... B88 X-Alpha parameter XAlpha .... 0.666667 Becke's b parameter XBeta .... 0.004200 Correlation Functional Correlation .... LYP LDA part of GGA corr. LDAOpt .... VWN-5 Gradients option PostSCFGGA .... off Hybrid DFT is turned on Fraction HF Exchange ScalHFX .... 0.200000 Scaling of DF-GGA-X ScalDFX .... 0.720000 Scaling of DF-GGA-C ScalDFC .... 0.810000 Scaling of DF-LDA-C ScalLDAC .... 1.000000 Perturbative correction .... 0.000000 NL short-range parameter .... 4.800000 RI-approximation to the Coulomb term is turned on Number of AuxJ basis functions .... 796 RIJ-COSX (HFX calculated with COS-X)).... on General Settings: Integral files IntName .... caffeine_tddft Hartree-Fock type HFTyp .... RHF Total Charge Charge .... 0 Multiplicity Mult .... 1 Number of Electrons NEL .... 102 Basis Dimension Dim .... 494 Nuclear Repulsion ENuc .... 929.7537421425 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 .... 1 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) .... 1.000e-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 Autom. constraints SOSCFAutoConstrain .... off 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 .... 2.500e-11 Eh Primitive CutOff TCut .... 2.500e-12 Eh Convergence Tolerance: Convergence Check Mode ConvCheckMode .... Total+1el-Energy Convergence forced ConvForced .... 1 Energy Change TolE .... 1.000e-08 Eh 1-El. energy change .... 1.000e-05 Eh Orbital Gradient TolG .... 1.000e-05 Orbital Rotation angle TolX .... 1.000e-05 DIIS Error TolErr .... 5.000e-07 --------------------- INITIAL GUESS: MOREAD --------------------- Guess MOs are being read from file: caffeine_tddft.ges Input Geometry matches current geometry (good) Input basis set matches current basis set (good) Occupation numbers will be reassigned to an Aufbau configuration MOs were renormalized MOs were reorthogonalized (Cholesky) ------------------ INITIAL GUESS DONE ( 0.1 sec) ------------------ ================================================================================ WARNING Check your MOs and check whether a frozen core calculation is appropriate MO 0 should be a O s semi-core orbital but seems to be delocalized with a C p orbital (85.3% vs. 3.5%) ================================================================================ ================================================================================ WARNING Check your MOs and check whether a frozen core calculation is appropriate MO 1 should be a O s semi-core orbital but seems to be delocalized with a C p orbital (89.7% vs. 16.0%) ================================================================================ ================================================================================ WARNING Check your MOs and check whether a frozen core calculation is appropriate MO 2 should be a N s semi-core orbital but seems to be delocalized with a C p orbital (89.5% vs. 5.3%) ================================================================================ ================================================================================ WARNING Check your MOs and check whether a frozen core calculation is appropriate MO 5 should be a N s semi-core orbital but seems to be delocalized with a C p orbital (88.2% vs. 10.2%) ================================================================================ ================================================================================ WARNING Check your MOs and check whether a frozen core calculation is appropriate MO 9 should be a C s semi-core orbital but seems to be delocalized with a N p orbital (83.2% vs. 19.0%) ================================================================================ ================================================================================ WARNING Check your MOs and check whether a frozen core calculation is appropriate MO 10 should be a C s semi-core orbital but seems to be delocalized with a C p orbital (55.5% vs. 19.4%) ================================================================================ ================================================================================ WARNING Check your MOs and check whether a frozen core calculation is appropriate MO 0 should be a O s semi-core orbital but seems to be delocalized with a C p orbital (85.3% vs. 3.5%) ================================================================================ ================================================================================ WARNING Check your MOs and check whether a frozen core calculation is appropriate MO 1 should be a O s semi-core orbital but seems to be delocalized with a C p orbital (89.7% vs. 16.0%) ================================================================================ ================================================================================ WARNING Check your MOs and check whether a frozen core calculation is appropriate MO 2 should be a N s semi-core orbital but seems to be delocalized with a C p orbital (89.5% vs. 5.3%) ================================================================================ ================================================================================ WARNING Check your MOs and check whether a frozen core calculation is appropriate MO 5 should be a N s semi-core orbital but seems to be delocalized with a C p orbital (88.2% vs. 10.2%) ================================================================================ ================================================================================ WARNING Check your MOs and check whether a frozen core calculation is appropriate MO 9 should be a C s semi-core orbital but seems to be delocalized with a N p orbital (83.2% vs. 19.0%) ================================================================================ ================================================================================ WARNING Check your MOs and check whether a frozen core calculation is appropriate MO 10 should be a C s semi-core orbital but seems to be delocalized with a C p orbital (55.5% vs. 19.4%) ================================================================================ **** ENERGY FILE WAS UPDATED (caffeine_tddft.en.tmp) **** Finished Guess after 0.7 sec Maximum memory used throughout the entire GUESS-calculation: 34.1 MB Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization 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specified Authorization required, but no authorization protocol specified ************************************************************ * Program running with 30 parallel MPI-processes * * working on a common directory * ************************************************************ ------------------------------------------------------------------------------------------- ORCA LEAN-SCF memory conserving SCF solver ------------------------------------------------------------------------------------------- ----------------------------------------D-I-I-S-------------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) ------------------------------------------------------------------------------------------- *** Starting incremental Fock matrix formation *** 1 -601.3255340283496935 0.00e+00 1.07e+01 3.60e+02 1.98e+00 0.700 1.8 Warning: op=0 Small HOMO/LUMO gap ( 0.085) - skipping pre-diagonalization Will do a full diagonalization 2 -625.8314168335925842 -2.45e+01 7.54e+00 2.54e+02 1.29e+00 0.700 1.2 3 -642.2776123457572339 -1.64e+01 5.28e+00 1.78e+02 8.81e-01 0.700 1.1 4 -653.6402693296001871 -1.14e+01 3.70e+00 1.24e+02 6.11e-01 0.700 1.1 5 -661.5932641444910587 -7.95e+00 2.59e+00 8.71e+01 4.28e-01 0.700 1.1 6 -667.1740071741182874 -5.58e+00 1.81e+00 6.10e+01 3.00e-01 0.700 1.1 7 -671.0897393322316020 -3.92e+00 1.27e+00 4.27e+01 2.10e-01 0.700 1.1 ***Turning on AO-DIIS*** 8 -673.8357821201195748 -2.75e+00 8.87e-01 2.99e+01 1.47e-01 0.700 1.1 9 -675.7604741952072800 -1.92e+00 6.21e-01 2.09e+01 1.03e-01 0.700 1.1 10 -677.1094470533873846 -1.35e+00 4.35e-01 1.46e+01 7.21e-02 0.700 1.0 11 -678.0545338046456436 -9.45e-01 1.01e+00 3.42e+01 5.05e-02 0.000 1.0 *** Initializing SOSCF *** ---------------------------------------S-O-S-C-F-------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) -------------------------------------------------------------------------------------- 12 -680.2622896337559268 -2.21e+00 2.09e-04 2.01e-03 1.89e-03 1.1 *** Restarting incremental Fock matrix formation *** 13 -680.2623361671292059 -4.65e-05 4.24e-04 2.78e-03 4.32e-04 1.6 14 -680.2623340590096177 2.11e-06 9.49e-05 7.65e-04 5.24e-04 1.3 15 -680.2623439859121390 -9.93e-06 7.41e-05 5.01e-04 1.30e-04 1.2 16 -680.2623435224725199 4.63e-07 2.86e-05 2.31e-04 1.37e-04 1.2 17 -680.2623445756355522 -1.05e-06 1.75e-05 2.14e-04 3.44e-05 1.1 18 -680.2623445166548208 5.90e-08 1.12e-05 1.46e-04 4.26e-05 1.1 19 -680.2623446215100103 -1.05e-07 2.47e-06 3.04e-05 4.79e-06 1.0 20 -680.2623446107413656 1.08e-08 1.78e-06 1.41e-05 1.02e-05 0.9 21 -680.2623446287029765 -1.80e-08 2.10e-06 2.03e-05 1.39e-06 0.8 *** Gradient check signals convergence *** ***************************************************** * SUCCESS * * SCF CONVERGED AFTER 21 CYCLES * ***************************************************** Recomputing exchange energy using gridx3 ... done ( 2.354 sec) Old exchange energy : -17.612847021 Eh New exchange energy : -17.612846045 Eh Exchange energy change after final integration : 0.000000976 Eh Total energy after final integration : -680.262343636 Eh **** ENERGY FILE WAS UPDATED (caffeine_tddft.en.tmp) **** ---------------- TOTAL SCF ENERGY ---------------- Total Energy : -680.26234363636229 Eh -18510.87945 eV Components: Nuclear Repulsion : 929.75374214253020 Eh 25299.88555 eV Electronic Energy : -1610.01608675498574 Eh -43810.76502 eV One Electron Energy: -2770.20994540335369 Eh -75381.24492 eV Two Electron Energy: 1160.19385864836795 Eh 31570.47991 eV Virial components: Potential Energy : -1357.63778475428308 Eh -36943.20228 eV Kinetic Energy : 677.37544111792090 Eh 18432.32283 eV Virial Ratio : 2.00426189428078 DFT components: N(Alpha) : 51.000068854961 electrons N(Beta) : 51.000068854961 electrons N(Total) : 102.000137709922 electrons E(X) : -70.079024742587 Eh E(C) : -4.158224552695 Eh E(XC) : -74.237249295282 Eh --------------- SCF CONVERGENCE --------------- Last Energy change ... 1.7962e-08 Tolerance : 1.0000e-08 Last MAX-Density change ... 2.0321e-05 Tolerance : 1.0000e-07 Last RMS-Density change ... 2.0992e-06 Tolerance : 5.0000e-09 Last DIIS Error ... 1.8906e-03 Tolerance : 5.0000e-07 Last Orbital Gradient ... 1.3919e-06 Tolerance : 1.0000e-05 Last Orbital Rotation ... 4.4484e-06 Tolerance : 1.0000e-05 ---------------- ORBITAL ENERGIES ---------------- NO OCC E(Eh) E(eV) 0 2.0000 -19.101164 -519.7691 1 2.0000 -19.096597 -519.6448 2 2.0000 -14.400432 -391.8557 3 2.0000 -14.377133 -391.2217 4 2.0000 -14.370617 -391.0444 5 2.0000 -14.320590 -389.6831 6 2.0000 -10.309761 -280.5428 7 2.0000 -10.290646 -280.0227 8 2.0000 -10.253567 -279.0137 9 2.0000 -10.253024 -278.9990 10 2.0000 -10.230148 -278.3765 11 2.0000 -10.213649 -277.9275 12 2.0000 -10.207110 -277.7496 13 2.0000 -10.196179 -277.4521 14 2.0000 -1.076470 -29.2922 15 2.0000 -1.051544 -28.6140 16 2.0000 -1.041881 -28.3510 17 2.0000 -0.974908 -26.5286 18 2.0000 -0.937947 -25.5228 19 2.0000 -0.908124 -24.7113 20 2.0000 -0.797601 -21.7038 21 2.0000 -0.742466 -20.2035 22 2.0000 -0.733741 -19.9661 23 2.0000 -0.712852 -19.3977 24 2.0000 -0.659064 -17.9340 25 2.0000 -0.644595 -17.5403 26 2.0000 -0.605391 -16.4735 27 2.0000 -0.585824 -15.9411 28 2.0000 -0.536712 -14.6047 29 2.0000 -0.511637 -13.9224 30 2.0000 -0.511307 -13.9134 31 2.0000 -0.485036 -13.1985 32 2.0000 -0.483096 -13.1457 33 2.0000 -0.457032 -12.4365 34 2.0000 -0.455998 -12.4083 35 2.0000 -0.455865 -12.4047 36 2.0000 -0.439447 -11.9580 37 2.0000 -0.431275 -11.7356 38 2.0000 -0.426475 -11.6050 39 2.0000 -0.424968 -11.5640 40 2.0000 -0.403489 -10.9795 41 2.0000 -0.395284 -10.7562 42 2.0000 -0.392996 -10.6940 43 2.0000 -0.390993 -10.6395 44 2.0000 -0.330922 -9.0048 45 2.0000 -0.310572 -8.4511 46 2.0000 -0.293868 -7.9966 47 2.0000 -0.288619 -7.8537 48 2.0000 -0.273583 -7.4446 49 2.0000 -0.267583 -7.2813 50 2.0000 -0.227049 -6.1783 51 0.0000 -0.039735 -1.0812 52 0.0000 0.014145 0.3849 53 0.0000 0.024256 0.6600 54 0.0000 0.028088 0.7643 55 0.0000 0.041215 1.1215 56 0.0000 0.058673 1.5966 57 0.0000 0.068345 1.8598 58 0.0000 0.079300 2.1579 59 0.0000 0.082916 2.2563 60 0.0000 0.096350 2.6218 61 0.0000 0.101447 2.7605 *Only the first 10 virtual orbitals were printed. ******************************** * MULLIKEN POPULATION ANALYSIS * ******************************** ----------------------- MULLIKEN ATOMIC CHARGES ----------------------- 0 N : -0.111916 1 C : 0.283189 2 N : -0.101291 3 C : 0.234492 4 C : -0.076923 5 C : 0.196337 6 N : -0.054578 7 C : 0.030600 8 N : -0.302862 9 C : -0.252428 10 O : -0.372574 11 O : -0.376483 12 C : -0.240739 13 C : -0.249564 14 H : 0.148601 15 H : 0.130653 16 H : 0.156170 17 H : 0.130380 18 H : 0.146149 19 H : 0.146598 20 H : 0.121861 21 H : 0.127297 22 H : 0.127654 23 H : 0.159376 Sum of atomic charges: 0.0000000 -------------------------------- MULLIKEN REDUCED ORBITAL CHARGES -------------------------------- 0 N s : 3.445772 s : 3.445772 pz : 1.524270 p : 3.583218 px : 1.045657 py : 1.013291 dz2 : 0.006157 d : 0.078094 dxz : 0.013919 dyz : 0.010418 dx2y2 : 0.025614 dxy : 0.021986 f0 : 0.000788 f : 0.004832 f+1 : 0.000619 f-1 : 0.000617 f+2 : 0.000381 f-2 : 0.000419 f+3 : 0.001196 f-3 : 0.000810 1 C s : 3.036632 s : 3.036632 pz : 0.841514 p : 2.371510 px : 0.768933 py : 0.761063 dz2 : 0.008610 d : 0.283283 dxz : 0.066523 dyz : 0.043337 dx2y2 : 0.087448 dxy : 0.077364 f0 : 0.002923 f : 0.025385 f+1 : 0.001806 f-1 : 0.001386 f+2 : 0.002911 f-2 : 0.003192 f+3 : 0.008800 f-3 : 0.004367 2 N s : 3.455798 s : 3.455798 pz : 1.520132 p : 3.558448 px : 1.007449 py : 1.030867 dz2 : 0.006175 d : 0.082054 dxz : 0.013665 dyz : 0.014231 dx2y2 : 0.022150 dxy : 0.025833 f0 : 0.000833 f : 0.004990 f+1 : 0.000598 f-1 : 0.000646 f+2 : 0.000429 f-2 : 0.000438 f+3 : 0.001258 f-3 : 0.000788 3 C s : 3.088937 s : 3.088937 pz : 0.816590 p : 2.389943 px : 0.812896 py : 0.760457 dz2 : 0.009288 d : 0.265546 dxz : 0.029256 dyz : 0.066258 dx2y2 : 0.036143 dxy : 0.124600 f0 : 0.002609 f : 0.021082 f+1 : 0.000965 f-1 : 0.001627 f+2 : 0.002908 f-2 : 0.001793 f+3 : 0.007512 f-3 : 0.003670 4 C s : 3.181964 s : 3.181964 pz : 1.132498 p : 2.756117 px : 0.748665 py : 0.874954 dz2 : 0.006766 d : 0.124369 dxz : 0.031808 dyz : 0.019741 dx2y2 : 0.031528 dxy : 0.034526 f0 : 0.002235 f : 0.014473 f+1 : 0.001475 f-1 : 0.000792 f+2 : 0.002274 f-2 : 0.000738 f+3 : 0.004088 f-3 : 0.002871 5 C s : 3.050673 s : 3.050673 pz : 0.950313 p : 2.549051 px : 0.739163 py : 0.859576 dz2 : 0.005883 d : 0.185386 dxz : 0.050118 dyz : 0.032984 dx2y2 : 0.049036 dxy : 0.047365 f0 : 0.002548 f : 0.018553 f+1 : 0.001768 f-1 : 0.000933 f+2 : 0.002255 f-2 : 0.002018 f+3 : 0.006087 f-3 : 0.002944 6 N s : 3.463603 s : 3.463603 pz : 1.424403 p : 3.489294 px : 1.044198 py : 1.020693 dz2 : 0.005930 d : 0.096238 dxz : 0.019808 dyz : 0.018200 dx2y2 : 0.025560 dxy : 0.026739 f0 : 0.000873 f : 0.005444 f+1 : 0.000551 f-1 : 0.000652 f+2 : 0.000715 f-2 : 0.000455 f+3 : 0.000787 f-3 : 0.001412 7 C s : 3.148212 s : 3.148212 pz : 0.965014 p : 2.672101 px : 0.947765 py : 0.759322 dz2 : 0.004208 d : 0.133671 dxz : 0.012998 dyz : 0.043903 dx2y2 : 0.047119 dxy : 0.025442 f0 : 0.002158 f : 0.015417 f+1 : 0.001132 f-1 : 0.001247 f+2 : 0.000524 f-2 : 0.002843 f+3 : 0.003571 f-3 : 0.003941 8 N s : 3.624998 s : 3.624998 pz : 1.210161 p : 3.611477 px : 0.987474 py : 1.413842 dz2 : 0.006102 d : 0.062664 dxz : 0.012509 dyz : 0.012091 dx2y2 : 0.014390 dxy : 0.017572 f0 : 0.000667 f : 0.003723 f+1 : 0.000357 f-1 : 0.000326 f+2 : 0.000194 f-2 : 0.000703 f+3 : 0.000778 f-3 : 0.000698 9 C s : 3.281826 s : 3.281826 pz : 1.079266 p : 2.899371 px : 1.085452 py : 0.734653 dz2 : 0.005699 d : 0.065158 dxz : 0.005505 dyz : 0.026686 dx2y2 : 0.012057 dxy : 0.015212 f0 : 0.000776 f : 0.006073 f+1 : 0.000943 f-1 : 0.000684 f+2 : 0.001250 f-2 : -0.000041 f+3 : 0.001005 f-3 : 0.001456 10 O s : 3.817411 s : 3.817411 pz : 1.465819 p : 4.522931 px : 1.382333 py : 1.674780 dz2 : 0.002863 d : 0.030418 dxz : 0.008964 dyz : 0.002057 dx2y2 : 0.008204 dxy : 0.008330 f0 : 0.000199 f : 0.001813 f+1 : 0.000173 f-1 : 0.000056 f+2 : 0.000196 f-2 : 0.000258 f+3 : 0.000519 f-3 : 0.000412 11 O s : 3.824119 s : 3.824119 pz : 1.453752 p : 4.521214 px : 1.761022 py : 1.306439 dz2 : 0.002635 d : 0.029432 dxz : 0.000138 dyz : 0.010427 dx2y2 : 0.008375 dxy : 0.007856 f0 : 0.000193 f : 0.001719 f+1 : 0.000025 f-1 : 0.000177 f+2 : 0.000405 f-2 : 0.000016 f+3 : 0.000512 f-3 : 0.000392 12 C s : 3.282829 s : 3.282829 pz : 1.097889 p : 2.885740 px : 0.989270 py : 0.798582 dz2 : 0.005328 d : 0.066277 dxz : 0.004289 dyz : 0.029371 dx2y2 : 0.016810 dxy : 0.010480 f0 : 0.000667 f : 0.005893 f+1 : 0.000388 f-1 : 0.001310 f+2 : 0.000305 f-2 : 0.000819 f+3 : 0.001322 f-3 : 0.001082 13 C s : 3.276279 s : 3.276279 pz : 1.076265 p : 2.903676 px : 0.823619 py : 1.003791 dz2 : 0.005234 d : 0.063485 dxz : 0.024753 dyz : 0.005648 dx2y2 : 0.016522 dxy : 0.011327 f0 : 0.000771 f : 0.006124 f+1 : 0.001279 f-1 : 0.000329 f+2 : 0.000092 f-2 : 0.001108 f+3 : 0.001218 f-3 : 0.001327 14 H s : 0.829719 s : 0.829719 pz : 0.004742 p : 0.021680 px : 0.014368 py : 0.002570 15 H s : 0.848012 s : 0.848012 pz : 0.010865 p : 0.021335 px : 0.006316 py : 0.004154 16 H s : 0.821686 s : 0.821686 pz : 0.004352 p : 0.022144 px : 0.012531 py : 0.005261 17 H s : 0.848283 s : 0.848283 pz : 0.009214 p : 0.021337 px : 0.007445 py : 0.004678 18 H s : 0.832474 s : 0.832474 pz : 0.009986 p : 0.021377 px : 0.004407 py : 0.006984 19 H s : 0.832020 s : 0.832020 pz : 0.010168 p : 0.021382 px : 0.005011 py : 0.006203 20 H s : 0.856812 s : 0.856812 pz : 0.004517 p : 0.021327 px : 0.013254 py : 0.003556 21 H s : 0.851383 s : 0.851383 pz : 0.010800 p : 0.021320 px : 0.006053 py : 0.004468 22 H s : 0.851029 s : 0.851029 pz : 0.009113 p : 0.021317 px : 0.007435 py : 0.004769 23 H s : 0.817597 s : 0.817597 pz : 0.004385 p : 0.023027 px : 0.005141 py : 0.013501 ******************************* * LOEWDIN POPULATION ANALYSIS * ******************************* ---------------------- LOEWDIN ATOMIC CHARGES ---------------------- 0 N : 0.233311 1 C : -0.444533 2 N : 0.240430 3 C : -0.388515 4 C : -0.165847 5 C : -0.251154 6 N : 0.261615 7 C : -0.249097 8 N : 0.107774 9 C : -0.246750 10 O : 0.074333 11 O : 0.065593 12 C : -0.243178 13 C : -0.254885 14 H : 0.135116 15 H : 0.122930 16 H : 0.128996 17 H : 0.122853 18 H : 0.127803 19 H : 0.127929 20 H : 0.122992 21 H : 0.121529 22 H : 0.121615 23 H : 0.129138 ------------------------------- LOEWDIN REDUCED ORBITAL CHARGES ------------------------------- 0 N s : 2.890816 s : 2.890816 pz : 1.325251 p : 3.584657 px : 1.132754 py : 1.126651 dz2 : 0.020119 d : 0.272743 dxz : 0.036643 dyz : 0.033725 dx2y2 : 0.095373 dxy : 0.086884 f0 : 0.001704 f : 0.018473 f+1 : 0.001695 f-1 : 0.001981 f+2 : 0.001905 f-2 : 0.002086 f+3 : 0.006429 f-3 : 0.002674 1 C s : 2.710803 s : 2.710803 pz : 0.809509 p : 2.638633 px : 0.938754 py : 0.890370 dz2 : 0.063929 d : 0.948481 dxz : 0.178335 dyz : 0.128145 dx2y2 : 0.297623 dxy : 0.280449 f0 : 0.008308 f : 0.146616 f+1 : 0.010841 f-1 : 0.008212 f+2 : 0.018927 f-2 : 0.021502 f+3 : 0.053226 f-3 : 0.025600 2 N s : 2.865243 s : 2.865243 pz : 1.323222 p : 3.580625 px : 1.130118 py : 1.127285 dz2 : 0.019266 d : 0.293453 dxz : 0.042026 dyz : 0.039618 dx2y2 : 0.089537 dxy : 0.103006 f0 : 0.001974 f : 0.020249 f+1 : 0.002118 f-1 : 0.001773 f+2 : 0.002187 f-2 : 0.002539 f+3 : 0.006704 f-3 : 0.002954 3 C s : 2.717385 s : 2.717385 pz : 0.778997 p : 2.661087 px : 0.915866 py : 0.966224 dz2 : 0.056456 d : 0.884946 dxz : 0.095215 dyz : 0.185985 dx2y2 : 0.209629 dxy : 0.337661 f0 : 0.007695 f : 0.125097 f+1 : 0.005862 f-1 : 0.010910 f+2 : 0.020550 f-2 : 0.011871 f+3 : 0.046892 f-3 : 0.021318 4 C s : 2.683936 s : 2.683936 pz : 0.988604 p : 2.853178 px : 0.870035 py : 0.994539 dz2 : 0.045809 d : 0.549518 dxz : 0.097192 dyz : 0.066075 dx2y2 : 0.179999 dxy : 0.160444 f0 : 0.005774 f : 0.079214 f+1 : 0.007338 f-1 : 0.004851 f+2 : 0.015598 f-2 : 0.004603 f+3 : 0.022838 f-3 : 0.018212 5 C s : 2.683438 s : 2.683438 pz : 0.866841 p : 2.741437 px : 0.883700 py : 0.990896 dz2 : 0.051946 d : 0.724158 dxz : 0.141135 dyz : 0.105269 dx2y2 : 0.209263 dxy : 0.216545 f0 : 0.006299 f : 0.102120 f+1 : 0.008545 f-1 : 0.005493 f+2 : 0.015683 f-2 : 0.012958 f+3 : 0.036326 f-3 : 0.016816 6 N s : 2.861548 s : 2.861548 pz : 1.245313 p : 3.525566 px : 1.131355 py : 1.148898 dz2 : 0.019130 d : 0.327765 dxz : 0.057971 dyz : 0.047284 dx2y2 : 0.101451 dxy : 0.101929 f0 : 0.001638 f : 0.023506 f+1 : 0.001733 f-1 : 0.002006 f+2 : 0.003867 f-2 : 0.002773 f+3 : 0.003115 f-3 : 0.008373 7 C s : 2.776386 s : 2.776386 pz : 0.912431 p : 2.816482 px : 0.980957 py : 0.923094 dz2 : 0.042440 d : 0.568666 dxz : 0.030380 dyz : 0.132876 dx2y2 : 0.227569 dxy : 0.135401 f0 : 0.005527 f : 0.087563 f+1 : 0.005341 f-1 : 0.007498 f+2 : 0.003547 f-2 : 0.018802 f+3 : 0.020410 f-3 : 0.026437 8 N s : 3.057631 s : 3.057631 pz : 1.104330 p : 3.610199 px : 1.109742 py : 1.396128 dz2 : 0.018150 d : 0.203449 dxz : 0.043601 dyz : 0.016237 dx2y2 : 0.053082 dxy : 0.072379 f0 : 0.001282 f : 0.020946 f+1 : 0.001948 f-1 : 0.001099 f+2 : 0.000859 f-2 : 0.004028 f+3 : 0.006182 f-3 : 0.005549 9 C s : 2.833144 s : 2.833144 pz : 1.103860 p : 3.068199 px : 1.100716 py : 0.863623 dz2 : 0.042406 d : 0.306089 dxz : 0.034950 dyz : 0.092087 dx2y2 : 0.070911 dxy : 0.065735 f0 : 0.004288 f : 0.039318 f+1 : 0.003314 f-1 : 0.005428 f+2 : 0.008080 f-2 : 0.002232 f+3 : 0.007267 f-3 : 0.008709 10 O s : 3.395873 s : 3.395873 pz : 1.380569 p : 4.455538 px : 1.492753 py : 1.582217 dz2 : 0.008274 d : 0.068019 dxz : 0.014581 dyz : 0.003227 dx2y2 : 0.020131 dxy : 0.021806 f0 : 0.000556 f : 0.006237 f+1 : 0.000854 f-1 : 0.000252 f+2 : 0.000484 f-2 : 0.000623 f+3 : 0.001618 f-3 : 0.001850 11 O s : 3.400674 s : 3.400674 pz : 1.370047 p : 4.461082 px : 1.620401 py : 1.470634 dz2 : 0.007988 d : 0.066704 dxz : 0.000193 dyz : 0.015678 dx2y2 : 0.024715 dxy : 0.018129 f0 : 0.000502 f : 0.005947 f+1 : 0.000103 f-1 : 0.000962 f+2 : 0.000877 f-2 : 0.000049 f+3 : 0.001675 f-3 : 0.001779 12 C s : 2.833783 s : 2.833783 pz : 1.108282 p : 3.066245 px : 1.040270 py : 0.917693 dz2 : 0.040926 d : 0.304334 dxz : 0.015286 dyz : 0.111364 dx2y2 : 0.081880 dxy : 0.054878 f0 : 0.004038 f : 0.038815 f+1 : 0.003816 f-1 : 0.005503 f+2 : 0.002447 f-2 : 0.006948 f+3 : 0.008370 f-3 : 0.007693 13 C s : 2.834275 s : 2.834275 pz : 1.102819 p : 3.073850 px : 0.927673 py : 1.043358 dz2 : 0.042454 d : 0.307484 dxz : 0.106266 dyz : 0.018174 dx2y2 : 0.075979 dxy : 0.064610 f0 : 0.004196 f : 0.039276 f+1 : 0.005000 f-1 : 0.003629 f+2 : 0.002088 f-2 : 0.008047 f+3 : 0.008238 f-3 : 0.008079 14 H s : 0.803744 s : 0.803744 pz : 0.014375 p : 0.061140 px : 0.038723 py : 0.008042 15 H s : 0.815388 s : 0.815388 pz : 0.031869 p : 0.061683 px : 0.018727 py : 0.011086 16 H s : 0.806907 s : 0.806907 pz : 0.013876 p : 0.064098 px : 0.036875 py : 0.013346 17 H s : 0.815485 s : 0.815485 pz : 0.027422 p : 0.061662 px : 0.021911 py : 0.012329 18 H s : 0.810205 s : 0.810205 pz : 0.029920 p : 0.061992 px : 0.013394 py : 0.018679 19 H s : 0.810037 s : 0.810037 pz : 0.030085 p : 0.062034 px : 0.015323 py : 0.016625 20 H s : 0.816193 s : 0.816193 pz : 0.014059 p : 0.060815 px : 0.036121 py : 0.010634 21 H s : 0.816728 s : 0.816728 pz : 0.031691 p : 0.061743 px : 0.016344 py : 0.013708 22 H s : 0.816603 s : 0.816603 pz : 0.027114 p : 0.061782 px : 0.019961 py : 0.014706 23 H s : 0.804205 s : 0.804205 pz : 0.013968 p : 0.066657 px : 0.014383 py : 0.038306 ***************************** * 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 N 7.1119 7.0000 -0.1119 3.1734 3.1734 -0.0000 1 C 5.7168 6.0000 0.2832 4.3030 4.3030 -0.0000 2 N 7.1013 7.0000 -0.1013 3.2634 3.2634 -0.0000 3 C 5.7655 6.0000 0.2345 4.3116 4.3116 0.0000 4 C 6.0769 6.0000 -0.0769 3.6739 3.6739 -0.0000 5 C 5.8037 6.0000 0.1963 4.0383 4.0383 -0.0000 6 N 7.0546 7.0000 -0.0546 3.3890 3.3890 0.0000 7 C 5.9694 6.0000 0.0306 4.0006 4.0006 0.0000 8 N 7.3029 7.0000 -0.3029 3.0828 3.0828 0.0000 9 C 6.2524 6.0000 -0.2524 3.8380 3.8380 0.0000 10 O 8.3726 8.0000 -0.3726 2.1422 2.1422 -0.0000 11 O 8.3765 8.0000 -0.3765 2.1425 2.1425 0.0000 12 C 6.2407 6.0000 -0.2407 3.8506 3.8506 0.0000 13 C 6.2496 6.0000 -0.2496 3.8222 3.8222 0.0000 14 H 0.8514 1.0000 0.1486 0.9721 0.9721 0.0000 15 H 0.8693 1.0000 0.1307 0.9666 0.9666 0.0000 16 H 0.8438 1.0000 0.1562 0.9782 0.9782 0.0000 17 H 0.8696 1.0000 0.1304 0.9665 0.9665 0.0000 18 H 0.8539 1.0000 0.1461 0.9645 0.9645 0.0000 19 H 0.8534 1.0000 0.1466 0.9648 0.9648 0.0000 20 H 0.8781 1.0000 0.1219 0.9611 0.9611 0.0000 21 H 0.8727 1.0000 0.1273 0.9687 0.9687 0.0000 22 H 0.8723 1.0000 0.1277 0.9688 0.9688 0.0000 23 H 0.8406 1.0000 0.1594 0.9826 0.9826 0.0000 Mayer bond orders larger than 0.100000 B( 0-N , 1-C ) : 1.1343 B( 0-N , 3-C ) : 1.1356 B( 0-N , 13-C ) : 0.9033 B( 1-C , 2-N ) : 1.1429 B( 1-C , 10-O ) : 1.9837 B( 2-N , 5-C ) : 1.1514 B( 2-N , 9-C ) : 0.9060 B( 3-C , 4-C ) : 1.0643 B( 3-C , 11-O ) : 2.0120 B( 4-C , 5-C ) : 1.4117 B( 4-C , 6-N ) : 1.1360 B( 5-C , 8-N ) : 1.3780 B( 6-N , 7-C ) : 1.3057 B( 6-N , 12-C ) : 0.9099 B( 7-C , 8-N ) : 1.5725 B( 7-C , 14-H ) : 0.9525 B( 9-C , 15-H ) : 0.9664 B( 9-C , 16-H ) : 0.9599 B( 9-C , 17-H ) : 0.9665 B( 12-C , 18-H ) : 0.9643 B( 12-C , 19-H ) : 0.9643 B( 12-C , 20-H ) : 0.9605 B( 13-C , 21-H ) : 0.9678 B( 13-C , 22-H ) : 0.9677 B( 13-C , 23-H ) : 0.9571 ------- TIMINGS ------- Total SCF time: 0 days 0 hours 0 min 27 sec Total time .... 27.790 sec Sum of individual times .... 27.083 sec ( 97.5%) SCF preparation .... 0.628 sec ( 2.3%) Fock matrix formation .... 23.602 sec ( 84.9%) Startup .... 0.041 sec ( 0.2% of F) Split-RI-J .... 2.456 sec ( 10.4% of F) Chain of spheres X .... 17.718 sec ( 75.1% of F) XC integration .... 3.618 sec ( 15.3% of F) XC Preparation .... 0.000 sec ( 0.0% of XC) Basis function eval. .... 0.965 sec ( 26.7% of XC) Density eval. .... 1.093 sec ( 30.2% of XC) XC-Functional eval. .... 0.046 sec ( 1.3% of XC) XC-Potential eval. .... 0.916 sec ( 25.3% of XC) Diagonalization .... 0.000 sec ( 0.0%) Density matrix formation .... 0.283 sec ( 1.0%) Total Energy calculation .... 0.111 sec ( 0.4%) Population analysis .... 0.075 sec ( 0.3%) Orbital Transformation .... 0.218 sec ( 0.8%) Orbital Orthonormalization .... 0.000 sec ( 0.0%) DIIS solution .... 1.437 sec ( 5.2%) SOSCF solution .... 0.723 sec ( 2.6%) Finished LeanSCF after 27.8 sec Maximum memory used throughout the entire LEANSCF-calculation: 52.6 MB Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified ************************************************************ * Program running with 30 parallel MPI-processes * * working on a common directory * ************************************************************ ------------------------------------------------------------------------------ ORCA PROPERTY INTEGRAL CALCULATIONS ------------------------------------------------------------------------------ GBWName ... caffeine_tddft.gbw Number of atoms ... 24 Number of basis functions ... 494 Max core memory ... 4096 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 ( 24 nuclei) Choice of electric origin ... Center of mass Position of electric origin ... ( 0.0078, 0.0056, 0.0657) 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 ( 0.1 sec) Calculating integrals ... Angular Momentum (ElOri) done ( 0.1 sec) Property integrals calculated in 0.2 sec Maximum memory used throughout the entire PROPINT-calculation: 36.5 MB Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified ************************************************************ * Program running with 30 parallel MPI-processes * * working on a common directory * ************************************************************ ------------------------------------------------------------------------------ ORCA TD-DFT/TDA CALCULATION ------------------------------------------------------------------------------ Input orbitals are from ... caffeine_tddft.gbw CI-vector output ... caffeine_tddft.cis Solver ... FN-2001 Tamm-Dancoff approximation ... operative CIS-Integral strategy ... AO-integrals Integral handling ... AO integral Direct Max. core memory used ... 4096 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... 50 to 51...493 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-11 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 ... 17140 Total number of batches ... 281 Average number of points per batch ... 60 Average number of grid points per atom ... 714 --------------------- 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-11 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 ... 7861 Total number of batches ... 78 Average number of points per batch ... 100 Average number of grid points per atom ... 328 --------------- TD-DFT XC SETUP --------------- DFT calculation ... on Name of the grid file ... caffeine_tddft.grid_cis.tmp RI-approximation ... on Aux-basis dimension ... 0 Exchange functional (TD-DFT) ... B88 X-Alpha parameter XAlpha (TD-DFT) ... 0.666667 Becke's b parameter XBeta (TD-DFT) ... 0.004200 Correlation functional (TD-DFT) ... LYP LDA part of GGA corr. LDAOpt (TD-DFT) ... VWN-5 Hybrid DFT ... on Exchange mixing (TD-DFT) ... 0.200 GGA exch. scaling (TD-DFT) ... 0.720 GGA corr. scaling (TD-DFT) ... 0.810 Building densities ... done Calculating rho(r) on the grid ... done Building xc-kernel on the grid ... done *** TD-DFT CALCULATION INITIALIZED *** ------------------------ DAVIDSON-DIAGONALIZATION ------------------------ Dimension of the eigenvalue problem ... 16391 Number of roots to be determined ... 10 Maximum size of the expansion space ... 100 Maximum number of iterations ... 100 Convergence tolerance for the residual ... 2.500e-07 Convergence tolerance for the energies ... 2.500e-07 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 ... 100 ****Iteration 0**** Time for iteration : TOTAL=5.2 TRAFO=0.2 RIJ=0.8 COSX=3.0 XC=1.1 Size of expansion space: 30 Lowest Energy : 0.184854974093 Maximum Energy change : 0.256137487724 (vector 9) Maximum residual norm : 0.020679384720 ****Iteration 1**** Time for iteration : TOTAL=2.0 TRAFO=0.1 RIJ=0.4 COSX=1.1 XC=0.4 Size of expansion space: 40 Lowest Energy : 0.178319219256 Maximum Energy change : 0.017405412381 (vector 9) Maximum residual norm : 0.001480718423 ****Iteration 2**** Time for iteration : TOTAL=2.0 TRAFO=0.1 RIJ=0.4 COSX=1.1 XC=0.4 Size of expansion space: 50 Lowest Energy : 0.177621129249 Maximum Energy change : 0.001307646366 (vector 8) Maximum residual norm : 0.000118455078 ****Iteration 3**** Time for iteration : TOTAL=2.1 TRAFO=0.1 RIJ=0.4 COSX=1.2 XC=0.4 Size of expansion space: 60 Lowest Energy : 0.177579908174 Maximum Energy change : 0.000201262222 (vector 8) Maximum residual norm : 0.000022936904 ****Iteration 4**** Time for iteration : TOTAL=2.0 TRAFO=0.1 RIJ=0.4 COSX=1.1 XC=0.4 Size of expansion space: 70 Lowest Energy : 0.177577563446 Maximum Energy change : 0.000034675950 (vector 8) Maximum residual norm : 0.000003531731 ****Iteration 5**** Time for iteration : TOTAL=2.0 TRAFO=0.1 RIJ=0.4 COSX=1.1 XC=0.4 Size of expansion space: 80 Lowest Energy : 0.177577443307 Maximum Energy change : 0.000210814845 (vector 9) Maximum residual norm : 0.000064423413 ****Iteration 6**** Time for iteration : TOTAL=2.0 TRAFO=0.1 RIJ=0.4 COSX=1.1 XC=0.4 Size of expansion space: 90 Lowest Energy : 0.177577440956 Maximum Energy change : 0.000075333438 (vector 9) Maximum residual norm : 0.000002347836 ****Iteration 7**** Time for iteration : TOTAL=2.0 TRAFO=0.1 RIJ=0.4 COSX=1.1 XC=0.4 Size of expansion space: 100 Lowest Energy : 0.177577440913 Maximum Energy change : 0.000002897017 (vector 9) Maximum residual norm : 0.000000100737 *** CONVERGENCE OF RESIDUAL NORM REACHED *** Storing the converged CI vectors ... caffeine_tddft.cis1 *** DAVIDSON DONE *** Total time for solving the CIS problem: 19.949sec ------------------------------------ TD-DFT/TDA EXCITED STATES (SINGLETS) ------------------------------------ the weight of the individual excitations are printed if larger than 1.0e-02 STATE 1: E= 0.177577 au 4.832 eV 38973.7 cm**-1 = 0.000000 Mult 1 47a -> 51a : 0.024271 (c= 0.15578993) 48a -> 51a : 0.010297 (c= -0.10147611) 48a -> 52a : 0.029053 (c= 0.17044858) 50a -> 51a : 0.882253 (c= -0.93928350) STATE 2: E= 0.182787 au 4.974 eV 40117.0 cm**-1 = 0.000000 Mult 1 46a -> 51a : 0.054733 (c= 0.23395073) 49a -> 51a : 0.905942 (c= 0.95180964) 49a -> 53a : 0.019357 (c= -0.13913119) STATE 3: E= 0.210001 au 5.714 eV 46089.9 cm**-1 = 0.000000 Mult 1 47a -> 51a : 0.083780 (c= 0.28944721) 48a -> 51a : 0.488519 (c= 0.69894110) 48a -> 52a : 0.016907 (c= -0.13002662) 50a -> 52a : 0.191229 (c= 0.43729761) 50a -> 53a : 0.196089 (c= -0.44281883) STATE 4: E= 0.220386 au 5.997 eV 48369.2 cm**-1 = 0.000000 Mult 1 45a -> 51a : 0.126233 (c= 0.35529353) 46a -> 51a : 0.820853 (c= 0.90600940) 49a -> 51a : 0.039212 (c= -0.19801935) STATE 5: E= 0.223722 au 6.088 eV 49101.3 cm**-1 = 0.000000 Mult 1 45a -> 51a : 0.016081 (c= -0.12680952) 50a -> 54a : 0.923560 (c= -0.96102009) 50a -> 55a : 0.043065 (c= -0.20752107) STATE 6: E= 0.224329 au 6.104 eV 49234.4 cm**-1 = 0.000000 Mult 1 47a -> 51a : 0.159960 (c= -0.39995031) 48a -> 51a : 0.329990 (c= 0.57444796) 48a -> 52a : 0.030064 (c= 0.17338883) 50a -> 52a : 0.430486 (c= -0.65611442) STATE 7: E= 0.226625 au 6.167 eV 49738.5 cm**-1 = 0.000000 Mult 1 45a -> 51a : 0.741594 (c= -0.86115856) 46a -> 51a : 0.102706 (c= 0.32047758) 46a -> 53a : 0.011485 (c= -0.10716771) 49a -> 51a : 0.031600 (c= -0.17776340) 49a -> 52a : 0.067534 (c= -0.25987281) 49a -> 53a : 0.017603 (c= -0.13267656) 50a -> 54a : 0.018153 (c= 0.13473190) STATE 8: E= 0.229925 au 6.257 eV 50462.7 cm**-1 = 0.000000 Mult 1 45a -> 51a : 0.065676 (c= -0.25627374) 46a -> 52a : 0.229723 (c= -0.47929435) 49a -> 52a : 0.683663 (c= 0.82683944) STATE 9: E= 0.231065 au 6.288 eV 50712.9 cm**-1 = 0.000000 Mult 1 47a -> 51a : 0.093026 (c= -0.30500222) 48a -> 51a : 0.094647 (c= 0.30764809) 50a -> 52a : 0.202925 (c= 0.45047146) 50a -> 53a : 0.531712 (c= 0.72918568) STATE 10: E= 0.238408 au 6.487 eV 52324.6 cm**-1 = 0.000000 Mult 1 47a -> 51a : 0.564163 (c= 0.75110784) 47a -> 52a : 0.013106 (c= -0.11448314) 48a -> 51a : 0.031079 (c= 0.17629307) 50a -> 51a : 0.013613 (c= 0.11667274) 50a -> 52a : 0.100349 (c= -0.31677906) 50a -> 53a : 0.198906 (c= 0.44598920) Storing amplitudes in GBW file ... ... GBW file created ----------------------------- TD-DFT/TDA-EXCITATION SPECTRA ----------------------------- Center of mass = ( 0.0078, 0.0056, 0.0657) 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 4.832128 38973.7 256.6 0.162204719 1.37015 0.50550 1.05570 0.01118 0-1A -> 2-1A 4.973880 40117.0 249.3 0.000094667 0.00078 0.00079 -0.00262 0.02774 0-1A -> 3-1A 5.714423 46089.9 217.0 0.017515644 0.12511 -0.27151 0.22431 0.03283 0-1A -> 4-1A 5.997017 48369.2 206.7 0.000240572 0.00164 -0.00018 -0.00002 0.04046 0-1A -> 5-1A 6.087781 49101.3 203.7 0.006869797 0.04606 -0.03328 0.01491 -0.21150 0-1A -> 6-1A 6.104293 49234.4 203.1 0.140840946 0.94175 -0.92552 0.27654 0.09318 0-1A -> 7-1A 6.166793 49738.5 201.1 0.000012226 0.00008 0.00193 0.00007 -0.00879 0-1A -> 8-1A 6.256579 50462.7 198.2 0.000033049 0.00022 -0.00283 -0.00834 -0.01175 0-1A -> 9-1A 6.287600 50712.9 197.2 0.050501324 0.32784 0.17656 0.54452 0.01283 0-1A -> 10-1A 6.487421 52324.6 191.1 0.521479505 3.28101 -1.80479 -0.02401 0.15219 ---------------------------------------------------------------------------------------------------- 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 4.832128 38973.7 256.6 0.012188168 0.00325 0.00060 0.05691 0.00272 0-1A -> 2-1A 4.973880 40117.0 249.3 0.002260738 0.00062 0.00208 -0.00125 0.02478 0-1A -> 3-1A 5.714423 46089.9 217.0 0.005048559 0.00159 0.03783 0.01239 -0.00235 0-1A -> 4-1A 5.997017 48369.2 206.7 0.002495706 0.00083 0.00253 -0.00133 0.02858 0-1A -> 5-1A 6.087781 49101.3 203.7 0.000004525 0.00000 0.00111 0.00038 -0.00038 0-1A -> 6-1A 6.104293 49234.4 203.1 0.012526239 0.00421 0.05802 0.02894 -0.00337 0-1A -> 7-1A 6.166793 49738.5 201.1 0.000001105 0.00000 -0.00028 -0.00006 -0.00054 0-1A -> 8-1A 6.256579 50462.7 198.2 0.000126604 0.00004 0.00085 -0.00026 0.00655 0-1A -> 9-1A 6.287600 50712.9 197.2 0.002116396 0.00073 -0.02304 -0.01418 0.00130 0-1A -> 10-1A 6.487421 52324.6 191.1 0.056594823 0.02024 0.13857 -0.02927 -0.01342 ------------------------------------------------------------------------------------------ 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 4.832128 38973.7 256.6 0.48643 0.03770 -0.02393 0.46266 0-1A -> 2-1A 4.973880 40117.0 249.3 -0.15845 0.02483 -0.30048 -0.01701 0-1A -> 3-1A 5.714423 46089.9 217.0 0.01851 -0.01641 0.00999 -0.20521 0-1A -> 4-1A 5.997017 48369.2 206.7 0.08258 0.04300 -0.03610 -0.00416 0-1A -> 5-1A 6.087781 49101.3 203.7 0.22417 -0.05011 -0.11757 0.00184 0-1A -> 6-1A 6.104293 49234.4 203.1 -0.95438 0.01884 -0.00907 0.23580 0-1A -> 7-1A 6.166793 49738.5 201.1 -0.06161 0.02916 -0.12507 -0.00943 0-1A -> 8-1A 6.256579 50462.7 198.2 0.33987 -0.36818 0.15672 0.03883 0-1A -> 9-1A 6.287600 50712.9 197.2 -0.07931 -0.01311 0.00649 -0.08197 0-1A -> 10-1A 6.487421 52324.6 191.1 3.56775 0.03536 -0.01507 0.36723 ------------------------------------------------------------------------------------------ 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 4.832128 38973.7 256.6 -0.21883 0.03770 -0.02393 0.46266 0-1A -> 2-1A 4.973880 40117.0 249.3 0.01436 0.02483 -0.30048 -0.01701 0-1A -> 3-1A 5.714423 46089.9 217.0 -0.03187 -0.01641 0.00999 -0.20521 0-1A -> 4-1A 5.997017 48369.2 206.7 0.08137 0.04300 -0.03610 -0.00416 0-1A -> 5-1A 6.087781 49101.3 203.7 -0.21238 -0.05011 -0.11757 0.00184 0-1A -> 6-1A 6.104293 49234.4 203.1 0.07646 0.01884 -0.00907 0.23580 0-1A -> 7-1A 6.166793 49738.5 201.1 0.00925 0.02916 -0.12507 -0.00943 0-1A -> 8-1A 6.256579 50462.7 198.2 -0.20415 -0.36818 0.15672 0.03883 0-1A -> 9-1A 6.287600 50712.9 197.2 0.21100 -0.01311 0.00649 -0.08197 0-1A -> 10-1A 6.487421 52324.6 191.1 0.81359 0.03536 -0.01507 0.36723 Total run time: 20.492 sec *** ORCA-CIS/TD-DFT FINISHED WITHOUT ERROR *** ----------------------- CIS/TD-DFT TOTAL ENERGY ----------------------- E(SCF) = -680.262343636 Eh DE(CIS) = 0.177577441 Eh (Root 1) ----------------------------- --------- E(tot) = -680.084766195 Eh Maximum memory used throughout the entire CIS-calculation: 271.8 MB => NOW LEAVING ORCA_CIS ------------------------- -------------------- FINAL SINGLE POINT ENERGY -680.084766195449 ------------------------- -------------------- Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified ************************************************************ * Program running with 30 parallel MPI-processes * * working on a common directory * ************************************************************ ------------------------------------------------------------------------------ ORCA PROPERTY CALCULATIONS ------------------------------------------------------------------------------ GBWName ... caffeine_tddft.gbw Number of atoms ... 24 Number of basis functions ... 494 Max core memory ... 4096 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 Static hyperpolarizability ... NO Atomic electric properties: Dipole moment ... NO Quadrupole moment ... NO Static polarizability ... NO Choice of electric origin ... Center of mass Position of electric origin ... 0.007801 0.005580 0.065744 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 SCF SOC stabilization energy ... NO Diagonal Born-Oppenheimer correction ... NO ------------- DIPOLE MOMENT ------------- Method : SCF Type of density : Electron Density Multiplicity : 1 Irrep : 0 Energy : -680.2623436363622886 Eh Basis : AO X Y Z Electronic contribution: -0.213832955 -0.959925457 -0.029506445 Nuclear contribution : -1.306385446 1.127430898 0.160717634 ----------------------------------------- Total Dipole Moment : -1.520218401 0.167505441 0.131211189 ----------------------------------------- Magnitude (a.u.) : 1.535036949 Magnitude (Debye) : 3.901753848 -------------------- Rotational spectrum -------------------- Rotational constants in cm-1: 0.035585 0.023487 0.014262 Rotational constants in MHz : 1066.809396 704.131670 427.551351 Dipole components along the rotational axes: x,y,z [a.u.] : 1.504582 -0.304256 -0.000471 x,y,z [Debye]: 3.824343 -0.773357 -0.001198 Dipole moment calculation done in 0.0 sec Maximum memory used throughout the entire PROP-calculation: 31.0 MB Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified Authorization required, but no authorization protocol specified -------------------------------- 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 caffeine_tddft.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 6.0 WIRES Comput. Molec. Sci. 2025 15(1), e70019 doi.org/10.1002/wcms.7019 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. Helmich-Paris, B.; de Souza, B.; Neese, F.; Izsák, R. An improved chain of spheres for exchange algorithm J. Chem. Phys. 2021 155(10), 104109 doi.org/10.1063/5.0058766 5. Neese, F. The SHARK Integral Generation and Digestion System J. Comp. Chem. 2022 44(3), 381 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(22), 224108 doi.org/10.1063/5.0004608 7. 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 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 ... 53.830 sec (= 0.897 min) Startup calculation ... 2.086 sec (= 0.035 min) 3.9 % SCF iterations ... 28.933 sec (= 0.482 min) 53.7 % Property integrals ... 0.883 sec (= 0.015 min) 1.6 % Property calculations ... 0.767 sec (= 0.013 min) 1.4 % CIS module ... 21.162 sec (= 0.353 min) 39.3 % ****ORCA TERMINATED NORMALLY**** TOTAL RUN TIME: 0 days 0 hours 0 minutes 54 seconds 544 msec