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 13:45:39 2026 * Host name: dirac.ttk.pte.hu * Process ID: 3726176 * Working dir.: /home/nora/SU/P4_nmr *********************************** *************************************** The coordinates will be read from file: methane_opt.xyz *************************************** Information: The global flag for NMR shieldings has been found ==>> will calculate the shieldings for all atoms in the system 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! ================================================================================ ================================================================================ INPUT FILE ================================================================================ NAME = methane_nmr.inp | 1> ! B3LYP def2-TZVP NMR TightSCF | 2> | 3> * xyzfile 0 1 methane_opt.xyz | 4> | 5> | 6> ****END OF INPUT**** ================================================================================ **************************** * Single Point Calculation * **************************** --------------------------------- CARTESIAN COORDINATES (ANGSTROEM) --------------------------------- H 0.534970 0.162888 0.946771 C -0.000025 -0.000009 -0.000021 H 0.207517 0.833601 -0.686475 H 0.338416 -0.942253 -0.454829 H -1.080978 -0.054327 0.194353 ---------------------------- CARTESIAN COORDINATES (A.U.) ---------------------------- NO LB ZA FRAG MASS X Y Z 0 H 1.0000 0 1.008 1.010947 0.307814 1.789138 1 C 6.0000 0 12.011 -0.000048 -0.000018 -0.000040 2 H 1.0000 0 1.008 0.392150 1.575278 -1.297249 3 H 1.0000 0 1.008 0.639514 -1.780601 -0.859502 4 H 1.0000 0 1.008 -2.042752 -0.102663 0.367275 -------------------------------- INTERNAL COORDINATES (ANGSTROEM) -------------------------------- H 0 0 0 0.000000000000 0.00000000 0.00000000 C 1 0 0 1.099623415780 0.00000000 0.00000000 H 2 1 0 1.099635820581 109.47321067 0.00000000 H 2 1 3 1.099643689263 109.46962403 119.99717971 H 2 1 3 1.099631841900 109.47425065 239.99769820 --------------------------- INTERNAL COORDINATES (A.U.) --------------------------- H 0 0 0 0.000000000000 0.00000000 0.00000000 C 1 0 0 2.077987106272 0.00000000 0.00000000 H 2 1 0 2.078010547948 109.47321067 0.00000000 H 2 1 3 2.078025417602 109.46962403 119.99717971 H 2 1 3 2.078003029331 109.47425065 239.99769820 --------------------- BASIS SET INFORMATION --------------------- There are 2 groups of distinct atoms Group 1 Type H : 5s1p contracted to 3s1p pattern {311/1} Group 2 Type C : 11s6p2d1f contracted to 5s3p2d1f pattern {62111/411/11/1} Atom 0H basis set group => 1 Atom 1C basis set group => 2 Atom 2H basis set group => 1 Atom 3H basis set group => 1 Atom 4H basis set group => 1 --------------------------------- AUXILIARY/J BASIS SET INFORMATION --------------------------------- There are 2 groups of distinct atoms Group 1 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} Group 2 Type C : 12s5p4d2f1g contracted to 6s4p3d1f1g pattern {711111/2111/211/2/1} Atom 0H basis set group => 1 Atom 1C basis set group => 2 Atom 2H basis set group => 1 Atom 3H basis set group => 1 Atom 4H basis set group => 1 ------------------------------------------------------------------------------ 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 ... 5 Number of basis functions ... 55 Number of shells ... 27 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 ... 93 # of shells in Aux-J ... 35 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 = 27 => 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 ... 378 Shell pairs after pre-screening ... 378 Total number of primitive shell pairs ... 1024 Primitive shell pairs kept ... 972 la=0 lb=0: 153 shell pairs la=1 lb=0: 119 shell pairs la=1 lb=1: 28 shell pairs la=2 lb=0: 34 shell pairs la=2 lb=1: 14 shell pairs la=2 lb=2: 3 shell pairs la=3 lb=0: 17 shell pairs la=3 lb=1: 7 shell pairs la=3 lb=2: 2 shell pairs la=3 lb=3: 1 shell pairs Checking whether 4 symmetric matrices of dimension 55 fit in memory :Max Core in MB = 4096.00 MB in use = 3.63 MB left = 4092.37 MB needed = 0.05 Data fit in memory = YES Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 13.317684174701 Eh Diagonalization of the overlap matrix: Smallest eigenvalue ... 1.512e-03 Time for diagonalization ... 0.000 sec Threshold for overlap eigenvalues ... 1.000e-07 Number of eigenvalues below threshold ... 0 Time for construction of square roots ... 0.000 sec Total time needed ... 0.001 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 ... 19255 Total number of batches ... 303 Average number of points per batch ... 63 Average number of grid points per atom ... 3851 -------------------- 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 ... 2530 Total number of batches ... 24 Average number of points per batch ... 105 Average number of grid points per atom ... 506 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 ... 5083 Total number of batches ... 43 Average number of points per batch ... 118 Average number of grid points per atom ... 1017 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 ... 11178 Total number of batches ... 91 Average number of points per batch ... 122 Average number of grid points per atom ... 2236 UseSFitting ... on Grids setup in 0.1 sec Initializing property integral containers ... done ( 0.0 sec) SHARK setup successfully completed in 0.2 seconds Maximum memory used throughout the entire STARTUP-calculation: 13.8 MB ------------------------------------------------------------------------------- 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 .... 93 RIJ-COSX (HFX calculated with COS-X)).... on General Settings: Integral files IntName .... methane_nmr Hartree-Fock type HFTyp .... RHF Total Charge Charge .... 0 Multiplicity Mult .... 1 Number of Electrons NEL .... 10 Basis Dimension Dim .... 55 Nuclear Repulsion ENuc .... 13.3176841747 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) .... 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 .... 0 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: 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 ( 0.0 sec) Making the grid ... done ( 0.0 sec) Mapping shells ... done Starting the XC term evaluation ... done ( 0.0 sec) promolecular density results # of electrons = 9.997666400 EX = -6.301353043 EC = -0.288089272 EX+EC = -6.589442315 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 ( 0.0 sec) ------------------ **** ENERGY FILE WAS UPDATED (methane_nmr.en.tmp) **** Finished Guess after 0.1 sec Maximum memory used throughout the entire GUESS-calculation: 7.4 MB ------------------------------------------------------------------------------------------- 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 -40.4188259977955369 0.00e+00 3.11e-03 4.41e-02 2.28e-01 0.700 0.2 2 -40.4582124089783974 -3.94e-02 2.21e-03 2.54e-02 1.16e-01 0.700 0.1 ***Turning on AO-DIIS*** 3 -40.4737273234301753 -1.55e-02 8.43e-04 7.95e-03 4.10e-02 0.700 0.1 4 -40.4824064334634954 -8.68e-03 1.24e-03 1.12e-02 1.79e-02 0.000 0.1 5 -40.5012207537992239 -1.88e-02 3.06e-04 2.42e-03 1.06e-02 0.000 0.1 *** Initializing SOSCF *** ---------------------------------------S-O-S-C-F-------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) -------------------------------------------------------------------------------------- 6 -40.5014061414666244 -1.85e-04 1.15e-04 9.80e-04 2.70e-03 0.1 *** Restarting incremental Fock matrix formation *** 7 -40.5014177301420233 -1.16e-05 7.80e-05 6.62e-04 2.72e-04 0.2 8 -40.5014177285466843 1.60e-09 2.17e-05 2.91e-04 2.54e-04 0.2 **** Energy Check signals convergence **** ***************************************************** * SUCCESS * * SCF CONVERGED AFTER 8 CYCLES * ***************************************************** Recomputing exchange energy using gridx3 ... done ( 0.242 sec) Old exchange energy : -1.313125308 Eh New exchange energy : -1.313190759 Eh Exchange energy change after final integration : -0.000065451 Eh Total energy after final integration : -40.501484158 Eh **** ENERGY FILE WAS UPDATED (methane_nmr.en.tmp) **** ---------------- TOTAL SCF ENERGY ---------------- Total Energy : -40.50148415753159 Eh -1102.10141 eV Components: Nuclear Repulsion : 13.31768417470091 Eh 362.39261 eV Electronic Energy : -53.81910288131537 Eh -1464.49224 eV One Electron Energy: -79.62169335556018 Eh -2166.61642 eV Two Electron Energy: 25.80259047424481 Eh 702.12418 eV Virial components: Potential Energy : -80.70920802240605 Eh -2196.20920 eV Kinetic Energy : 40.20772386487445 Eh 1094.10779 eV Virial Ratio : 2.00730606620868 DFT components: N(Alpha) : 5.000001580449 electrons N(Beta) : 5.000001580449 electrons N(Total) : 10.000003160899 electrons E(X) : -5.197425119876 Eh E(C) : -0.350688444501 Eh E(XC) : -5.548113564377 Eh --------------- SCF CONVERGENCE --------------- Last Energy change ... -1.5953e-09 Tolerance : 1.0000e-08 Last MAX-Density change ... 2.9092e-04 Tolerance : 1.0000e-07 Last RMS-Density change ... 2.1740e-05 Tolerance : 5.0000e-09 Last DIIS Error ... 2.7046e-03 Tolerance : 5.0000e-07 Last Orbital Gradient ... 2.5450e-04 Tolerance : 1.0000e-05 Last Orbital Rotation ... 1.6386e-04 Tolerance : 1.0000e-05 ---------------- ORBITAL ENERGIES ---------------- NO OCC E(Eh) E(eV) 0 2.0000 -10.154718 -276.3239 1 2.0000 -0.690176 -18.7806 2 2.0000 -0.390480 -10.6255 3 2.0000 -0.390474 -10.6253 4 2.0000 -0.390468 -10.6252 5 0.0000 0.049399 1.3442 6 0.0000 0.123727 3.3668 7 0.0000 0.123733 3.3669 8 0.0000 0.123737 3.3670 9 0.0000 0.199674 5.4334 10 0.0000 0.199681 5.4336 11 0.0000 0.199694 5.4340 12 0.0000 0.392317 10.6755 13 0.0000 0.469372 12.7723 14 0.0000 0.469382 12.7725 15 0.0000 0.469389 12.7727 *Only the first 10 virtual orbitals were printed. ******************************** * MULLIKEN POPULATION ANALYSIS * ******************************** ----------------------- MULLIKEN ATOMIC CHARGES ----------------------- 0 H : 0.116047 1 C : -0.464258 2 H : 0.116058 3 H : 0.116064 4 H : 0.116089 Sum of atomic charges: -0.0000000 -------------------------------- MULLIKEN REDUCED ORBITAL CHARGES -------------------------------- 0 H s : 0.863200 s : 0.863200 pz : 0.010064 p : 0.020753 px : 0.006172 py : 0.004517 1 C s : 3.285838 s : 3.285838 pz : 1.053241 p : 3.159751 px : 1.053256 py : 1.053254 dz2 : 0.002737 d : 0.016943 dxz : 0.002994 dyz : 0.004650 dx2y2 : 0.005321 dxy : 0.001241 f0 : 0.000113 f : 0.001727 f+1 : 0.000374 f-1 : 0.000123 f+2 : 0.000743 f-2 : -0.000013 f+3 : 0.000412 f-3 : -0.000024 2 H s : 0.863190 s : 0.863190 pz : 0.007351 p : 0.020753 px : 0.004622 py : 0.008779 3 H s : 0.863185 s : 0.863185 pz : 0.005667 p : 0.020751 px : 0.005077 py : 0.010007 4 H s : 0.863160 s : 0.863160 pz : 0.004588 p : 0.020751 px : 0.011797 py : 0.004366 ******************************* * LOEWDIN POPULATION ANALYSIS * ******************************* ---------------------- LOEWDIN ATOMIC CHARGES ---------------------- 0 H : 0.102594 1 C : -0.410395 2 H : 0.102598 3 H : 0.102601 4 H : 0.102603 ------------------------------- LOEWDIN REDUCED ORBITAL CHARGES ------------------------------- 0 H s : 0.835915 s : 0.835915 pz : 0.029850 p : 0.061491 px : 0.018282 py : 0.013359 1 C s : 2.906387 s : 2.906387 pz : 1.124722 p : 3.374169 px : 1.124723 py : 1.124723 dz2 : 0.019013 d : 0.117677 dxz : 0.020807 dyz : 0.032294 dx2y2 : 0.036951 dxy : 0.008612 f0 : 0.001691 f : 0.012162 f+1 : 0.002882 f-1 : 0.000758 f+2 : 0.001639 f-2 : 0.001656 f+3 : 0.002596 f-3 : 0.000941 2 H s : 0.835913 s : 0.835913 pz : 0.021788 p : 0.061489 px : 0.013671 py : 0.026030 3 H s : 0.835912 s : 0.835912 pz : 0.016776 p : 0.061488 px : 0.015026 py : 0.029686 4 H s : 0.835908 s : 0.835908 pz : 0.013571 p : 0.061490 px : 0.035007 py : 0.012911 ***************************** * 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 H 0.8840 1.0000 0.1160 0.9678 0.9678 -0.0000 1 C 6.4643 6.0000 -0.4643 3.9046 3.9046 -0.0000 2 H 0.8839 1.0000 0.1161 0.9678 0.9678 -0.0000 3 H 0.8839 1.0000 0.1161 0.9678 0.9678 0.0000 4 H 0.8839 1.0000 0.1161 0.9678 0.9678 0.0000 Mayer bond orders larger than 0.100000 B( 0-H , 1-C ) : 0.9761 B( 1-C , 2-H ) : 0.9761 B( 1-C , 3-H ) : 0.9761 B( 1-C , 4-H ) : 0.9761 ------- TIMINGS ------- Total SCF time: 0 days 0 hours 0 min 1 sec Total time .... 1.597 sec Sum of individual times .... 1.424 sec ( 89.1%) SCF preparation .... 0.043 sec ( 2.7%) Fock matrix formation .... 1.372 sec ( 85.9%) Startup .... 0.000 sec ( 0.0% of F) Split-RI-J .... 0.052 sec ( 3.8% of F) Chain of spheres X .... 1.052 sec ( 76.7% of F) XC integration .... 0.429 sec ( 31.3% of F) Basis function eval. .... 0.188 sec ( 43.8% of XC) Density eval. .... 0.066 sec ( 15.3% of XC) XC-Functional eval. .... 0.057 sec ( 13.4% of XC) XC-Potential eval. .... 0.099 sec ( 23.2% of XC) Diagonalization .... 0.000 sec ( 0.0%) Density matrix formation .... 0.001 sec ( 0.1%) Total Energy calculation .... 0.000 sec ( 0.0%) Population analysis .... 0.001 sec ( 0.1%) Orbital Transformation .... 0.001 sec ( 0.1%) Orbital Orthonormalization .... 0.000 sec ( 0.0%) DIIS solution .... 0.004 sec ( 0.3%) SOSCF solution .... 0.001 sec ( 0.1%) Finished LeanSCF after 1.6 sec Maximum memory used throughout the entire LEANSCF-calculation: 6.8 MB ------------------------------------------------------------------------------ ORCA PROPERTY INTEGRAL CALCULATIONS ------------------------------------------------------------------------------ GBWName ... methane_nmr.gbw Number of atoms ... 5 Number of basis functions ... 55 Max core memory ... 4096 MB Dipole integrals ... YES Quadrupole integrals ... NO Linear momentum integrals ... NO Angular momentum integrals ... NO Higher moments length integrals ... NO Higher moments velocity integrals ... NO Kinetic energy integrals ... NO GIAO right hand sides ... YES 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 ( 5 nuclei) Choice of electric origin ... Center of mass Position of electric origin ... ( -0.0000, -0.0000, -0.0001) 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 ... GIAO Right Hand Sides -> RIJCOSX used in SCF. Same chosen for GIAO calculation. One-electron GIAO integrals (SHARK) ... done ( 0.0 sec) Calculating G(B)[P] ... (RI-J: SHARK-ok) (COSX-ok) (add-J+K:ok) => dG/dB done ( 0.2 sec) DFT XC-terms ... done ( 0.3 sec) Extracting occupied and virtual blocks ... Operator 0 NO= 5 NV= 50 Transforming and RHS contribution ... done Adding eps_i * S(B)_ai terms ... done Projecting overlap derivatives ... done ( 0.0 sec) Building G[dS/dB_ij] (COSX) ... done ( 0.0 sec) Transforming to MO basis ... done Summing G[dS/dB_ij] into RHS contribs. ... done GIAO Right hand sides done ( 0.5 sec) Property integrals calculated in 0.6 sec Maximum memory used throughout the entire PROPINT-calculation: 9.1 MB ------------------------- -------------------- FINAL SINGLE POINT ENERGY -40.501484157532 ------------------------- -------------------- ------------------------------------------------------------------------------ ORCA SCF RESPONSE CALCULATION ------------------------------------------------------------------------------ GBWName ... methane_nmr.gbw Number of atoms ... 5 Number of basis functions ... 55 Max core memory ... 4096 MB Electric field perturbation ... NO Quadrupolar field perturbation ... NO Magnetic field perturbation (no GIAO) ... NO Magnetic field perturbation (with GIAO) ... YES Linear momentum (velocity) perturbation ... NO Spin-orbit coupling perturbation ... NO Choice of electric origin ... Center of mass Position of electric origin ... -0.000045 -0.000024 -0.000051 Choice of magnetic origin ... GIAO Position of magnetic origin ... 0.000000 0.000000 0.000000 Nuclear geometric perturbations ... NO ( 15 perturbations) Nucleus-orbit perturbations ... NO ( 0 perturbations) Spin-dipole/Fermi contact perturbations ... NO ( 0 perturbations) Total number of real perturbations ... 0 Total number of imaginary perturbations ... 3 Total number of triplet perturbations ... 0 Total number of SOC perturbations ... 0 *************************** * IMAGINARY PERTURBATIONS * *************************** ------------------- SHARK CP-SCF DRIVER ------------------- Dimension of the orbital basis ... 55 Dimension of the CPSCF-problem ... 250 Number of operators ... 1 Max. number of iterations ... 128 Convergence Tolerance ... 1.0e-04 Number of perturbations ... 3 Perturbation type ... IMAGINARY ---------------------------- POPLE LINEAR EQUATION SOLVER ---------------------------- ITERATION 0: ||err||_max = 6.8894e-02 ( 0.1 sec 0/ 3 done) ITERATION 1: ||err||_max = 1.9853e-04 ( 0.1 sec 0/ 3 done) ITERATION 2: ||err||_max = 5.6322e-06 ( 0.1 sec 3/ 3 done) CP-SCF equations solved in 0.2 sec Response densities calculated in 0.0 sec Maximum memory used throughout the entire SCFRESP-calculation: 6.5 MB ------------------------------------------------------------------------------ ORCA PROPERTY CALCULATIONS ------------------------------------------------------------------------------ GBWName ... methane_nmr.gbw Number of atoms ... 5 Number of basis functions ... 55 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 ... -0.000045 -0.000024 -0.000051 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 ... YES ( 5 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 : -40.5014841575315856 Eh Basis : AO X Y Z Electronic contribution: -0.000025901 0.000043563 0.000070446 Nuclear contribution : 0.000018994 -0.000037345 -0.000066018 ----------------------------------------- Total Dipole Moment : -0.000006907 0.000006218 0.000004429 ----------------------------------------- Magnitude (a.u.) : 0.000010295 Magnitude (Debye) : 0.000026168 -------------------- Rotational spectrum -------------------- Rotational constants in cm-1: 5.186558 5.186451 5.186377 Rotational constants in MHz : 155489.096556 155485.879656 155483.662977 Dipole components along the rotational axes: x,y,z [a.u.] : -0.000005 0.000006 0.000006 x,y,z [Debye]: -0.000013 0.000016 0.000016 Dipole moment calculation done in 0.0 sec GIAO: Analytic para- and diamagnetic shielding integrals (SHARK) ... done ( 0.0 sec) ------------------- CHEMICAL SHIELDINGS (ppm) ------------------- Method : SCF Type of density : Electron Density Type of derivative : Magnetic Field (with GIAOs) (Direction=X) Multiplicity : 1 Irrep : 0 Basis : AO -------------- Nucleus 0H : -------------- Diamagnetic contribution to the shielding tensor (ppm) : 28.586 0.899 5.225 0.899 25.908 1.592 5.225 1.591 34.881 Paramagnetic contribution to the shielding tensor (ppm): 1.934 -0.274 -1.589 -0.275 2.748 -0.484 -1.590 -0.483 0.018 Total shielding tensor (ppm): 30.520 0.625 3.637 0.624 28.656 1.107 3.636 1.108 34.899 Diagonalized sT*s matrix: sDSO 25.634 25.634 38.108 iso= 29.792 sPSO 2.830 2.833 -0.963 iso= 1.567 --------------- --------------- --------------- Total 28.464 28.467 37.145 iso= 31.359 Orientation: X 0.5620724 0.6688273 0.4865640 Y 0.7013909 -0.6972116 0.1481443 Z -0.4383211 -0.2580037 0.8609929 -------------- Nucleus 1C : -------------- Diamagnetic contribution to the shielding tensor (ppm) : 247.375 -0.002 0.001 0.001 247.376 0.001 0.000 -0.001 247.376 Paramagnetic contribution to the shielding tensor (ppm): -59.547 0.001 0.009 -0.013 -59.553 -0.006 0.004 -0.002 -59.554 Total shielding tensor (ppm): 187.829 -0.002 0.010 -0.012 187.823 -0.005 0.004 -0.003 187.822 Diagonalized sT*s matrix: sDSO 247.375 247.376 247.376 iso= 247.376 sPSO -59.558 -59.557 -59.539 iso= -59.551 --------------- --------------- --------------- Total 187.817 187.819 187.837 iso= 187.825 Orientation: X -0.6021931 0.2852478 0.7456521 Y -0.1937436 0.8538553 -0.4831092 Z 0.7744849 0.4353904 0.4589209 -------------- Nucleus 2H : -------------- Diamagnetic contribution to the shielding tensor (ppm) : 26.078 1.784 -1.469 1.785 32.802 -5.903 -1.470 -5.903 30.495 Paramagnetic contribution to the shielding tensor (ppm): 2.697 -0.542 0.448 -0.542 0.650 1.795 0.447 1.795 1.352 Total shielding tensor (ppm): 28.774 1.242 -1.022 1.243 33.452 -4.107 -1.023 -4.108 31.847 Diagonalized sT*s matrix: sDSO 25.634 25.633 38.107 iso= 29.791 sPSO 2.830 2.832 -0.963 iso= 1.566 --------------- --------------- --------------- Total 28.464 28.465 37.144 iso= 31.358 Orientation: X -0.5261676 0.8291645 -0.1887695 Y 0.6148075 0.2175563 -0.7580772 Z 0.5875027 0.5149325 0.6242476 -------------- Nucleus 3H : -------------- Diamagnetic contribution to the shielding tensor (ppm) : 26.815 -3.290 -1.588 -3.289 34.792 4.421 -1.588 4.420 27.767 Paramagnetic contribution to the shielding tensor (ppm): 2.472 1.002 0.482 1.001 0.045 -1.344 0.483 -1.345 2.183 Total shielding tensor (ppm): 29.286 -2.288 -1.106 -2.289 34.837 3.077 -1.105 3.075 29.950 Diagonalized sT*s matrix: sDSO 25.633 25.633 38.107 iso= 29.791 sPSO 2.831 2.832 -0.963 iso= 1.567 --------------- --------------- --------------- Total 28.464 28.465 37.144 iso= 31.358 Orientation: X 0.7902834 0.5298616 -0.3077318 Y -0.0119166 0.5154168 0.8568567 Z 0.6126257 -0.6734925 0.4136395 -------------- Nucleus 4H : -------------- Diamagnetic contribution to the shielding tensor (ppm) : 37.687 0.606 -2.168 0.606 25.664 -0.109 -2.168 -0.109 26.023 Paramagnetic contribution to the shielding tensor (ppm): -0.835 -0.185 0.659 -0.185 2.823 0.032 0.660 0.033 2.713 Total shielding tensor (ppm): 36.852 0.421 -1.508 0.421 28.486 -0.077 -1.508 -0.076 28.736 Diagonalized sT*s matrix: sDSO 25.633 25.633 38.107 iso= 29.791 sPSO 2.831 2.833 -0.963 iso= 1.567 --------------- --------------- --------------- Total 28.464 28.466 37.144 iso= 31.358 Orientation: X 0.0958518 0.1565058 -0.9830149 Y 0.6833323 -0.7284381 -0.0493442 Z 0.7237882 0.6669961 0.1767676 -------------------------------- CHEMICAL SHIELDING SUMMARY (ppm) -------------------------------- Nucleus Element Isotropic Anisotropy ------- ------- ------------ ------------ 0 H 31.359 8.679 1 C 187.825 0.019 2 H 31.358 8.680 3 H 31.358 8.679 4 H 31.358 8.679 NMR shielding tensor and spin rotation calculation done in 0.0 sec Maximum memory used throughout the entire PROP-calculation: 7.7 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 methane_nmr.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. 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 2. 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 3. Stoychev, G.L.; Auer, A.A.; Izsak, R.; Neese, F. Self-Consistent Field Calculation of Nuclear Magnetic Resonance Chemical Shielding Constants Using Gauge-Including Atomic Orbitals and Approximate Two-Electron Integrals J. Chem. Theory Comput. 2018 14(2), 619-637 doi.org/10.1021/acs.jctc.7b01006 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 ... 2.748 sec (= 0.046 min) Startup calculation ... 0.168 sec (= 0.003 min) 6.1 % SCF iterations ... 1.682 sec (= 0.028 min) 61.2 % Property integrals ... 0.591 sec (= 0.010 min) 21.5 % SCF Response ... 0.242 sec (= 0.004 min) 8.8 % Property calculations ... 0.065 sec (= 0.001 min) 2.4 % ****ORCA TERMINATED NORMALLY**** TOTAL RUN TIME: 0 days 0 hours 0 minutes 2 seconds 826 msec