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: Mon Jul 6 11:47:34 2026 * Host name: dirac.ttk.pte.hu * Process ID: 2475595 * Working dir.: /home/nora/SU/P1_opt *********************************** 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-SVP 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: Geometry Optimization ===> : Switching off AutoStart For restart on a previous wavefunction, please use MOREAD ================================================================================ INPUT FILE ================================================================================ NAME = water_opt_2.inp | 1> ! B3LYP def2-SVP Opt | 2> | 3> * xyz 0 1 | 4> O 0.000000 0.200000 0.000000 | 5> H 1.200000 0.000000 0.000000 | 6> H -1.200000 0.000000 0.000000 | 7> * | 8> | 9> ****END OF INPUT**** ================================================================================ ***************************** * Geometry Optimization Run * ***************************** Geometry optimization settings: Update method Update .... BFGS Choice of coordinates CoordSys .... (2022) Redundant Internals Initial Hessian InHess .... Almloef's Model Max. no of cycles MaxIter .... 50 Convergence Tolerances: Energy Change TolE .... 5.0000e-06 Eh Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr Max. Displacement TolMAXD .... 4.0000e-03 bohr RMS Displacement TolRMSD .... 2.0000e-03 bohr Strict Convergence .... False ------------------------------------------------------------------------------ ORCA OPTIMIZATION COORDINATE SETUP ------------------------------------------------------------------------------ The optimization will be done in redundant internal coordinates (2022) Making redundant internal coordinates ... (2022 redundants) done Evaluating the initial hessian ... (Almloef) done Evaluating the coordinates ... done Calculating the B-matrix .... done Calculating the G-matrix .... done The number of degrees of freedom .... 3 ----------------------------------------------------------------- Redundant Internal Coordinates ----------------------------------------------------------------- Definition Initial Value Approx d2E/dq ----------------------------------------------------------------- 1. B(H 1,O 0) 1.2166 0.202607 2. B(H 2,O 0) 1.2166 0.202607 3. A(H 1,O 0,H 2) 161.0754 0.240971 ----------------------------------------------------------------- Number of atoms .... 3 Number of degrees of freedom .... 3 ************************************************************* * GEOMETRY OPTIMIZATION CYCLE 1 * ************************************************************* --------------------------------- CARTESIAN COORDINATES (ANGSTROEM) --------------------------------- O 0.000000 0.200000 0.000000 H 1.200000 0.000000 0.000000 H -1.200000 0.000000 0.000000 ---------------------------- CARTESIAN COORDINATES (A.U.) ---------------------------- NO LB ZA FRAG MASS X Y Z 0 O 8.0000 0 15.999 0.000000 0.377945 0.000000 1 H 1.0000 0 1.008 2.267671 0.000000 0.000000 2 H 1.0000 0 1.008 -2.267671 0.000000 0.000000 -------------------------------- INTERNAL COORDINATES (ANGSTROEM) -------------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 H 1 0 0 1.216552506060 0.00000000 0.00000000 H 1 2 0 1.216552506060 161.07535558 0.00000000 --------------------------- INTERNAL COORDINATES (A.U.) --------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 H 1 0 0 2.298951063988 0.00000000 0.00000000 H 1 2 0 2.298951063988 161.07535558 0.00000000 --------------------- BASIS SET INFORMATION --------------------- There are 2 groups of distinct atoms Group 1 Type O : 7s4p1d contracted to 3s2p1d pattern {511/31/1} Group 2 Type H : 4s1p contracted to 2s1p pattern {31/1} Atom 0O basis set group => 1 Atom 1H basis set group => 2 Atom 2H basis set group => 2 --------------------------------- AUXILIARY/J BASIS SET INFORMATION --------------------------------- There are 2 groups of distinct atoms Group 1 Type O : 12s5p4d2f1g contracted to 6s4p3d1f1g pattern {711111/2111/211/2/1} Group 2 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} Atom 0O basis set group => 1 Atom 1H basis set group => 2 Atom 2H basis set group => 2 ------------------------------------------------------------------------------ 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 ... 3 Number of basis functions ... 24 Number of shells ... 12 Maximum angular momentum ... 2 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 ... 71 # of shells in Aux-J ... 25 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 = 12 => 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 ... 78 Shell pairs after pre-screening ... 78 Total number of primitive shell pairs ... 272 Primitive shell pairs kept ... 259 la=0 lb=0: 28 shell pairs la=1 lb=0: 28 shell pairs la=1 lb=1: 10 shell pairs la=2 lb=0: 7 shell pairs la=2 lb=1: 4 shell pairs la=2 lb=2: 1 shell pairs Checking whether 4 symmetric matrices of dimension 24 fit in memory :Max Core in MB = 4096.00 MB in use = 3.23 MB left = 4092.77 MB needed = 0.01 Data fit in memory = YES Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 7.180186275426 Eh Diagonalization of the overlap matrix: Smallest eigenvalue ... 7.484e-02 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 ... 0.000 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 ... 12772 Total number of batches ... 202 Average number of points per batch ... 63 Average number of grid points per atom ... 4257 -------------------- 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 ... 1664 Total number of batches ... 14 Average number of points per batch ... 118 Average number of grid points per atom ... 555 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 ... 3522 Total number of batches ... 30 Average number of points per batch ... 117 Average number of grid points per atom ... 1174 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 ... 7796 Total number of batches ... 62 Average number of points per batch ... 125 Average number of grid points per atom ... 2599 UseSFitting ... on Grids setup in 0.1 sec Initializing property integral containers ... done ( 0.0 sec) SHARK setup successfully completed in 0.1 seconds Maximum memory used throughout the entire STARTUP-calculation: 8.8 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 .... 71 RIJ-COSX (HFX calculated with COS-X)).... on General Settings: Integral files IntName .... water_opt_2 Hartree-Fock type HFTyp .... RHF Total Charge Charge .... 0 Multiplicity Mult .... 1 Number of Electrons NEL .... 10 Basis Dimension Dim .... 24 Nuclear Repulsion ENuc .... 7.1801862754 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 = 9.998953803 EX = -8.688843731 EC = -0.327092783 EX+EC = -9.015936514 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 (water_opt_2.en.tmp) **** Finished Guess after 0.0 sec Maximum memory used throughout the entire GUESS-calculation: 5.5 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 -76.0581420549937945 0.00e+00 1.52e-02 1.05e-01 3.74e-01 0.700 0.1 2 -76.1241088275504438 -6.60e-02 8.55e-03 5.81e-02 1.52e-01 0.700 0.0 ***Turning on AO-DIIS*** 3 -76.1437459111440518 -1.96e-02 2.64e-03 1.81e-02 3.36e-02 0.700 0.0 4 -76.1565895353797941 -1.28e-02 4.19e-03 2.46e-02 1.73e-02 0.000 0.0 5 -76.1874044107980950 -3.08e-02 8.95e-04 4.70e-03 8.17e-03 0.000 0.0 *** Initializing SOSCF *** ---------------------------------------S-O-S-C-F-------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) -------------------------------------------------------------------------------------- 6 -76.1875525944589924 -1.48e-04 4.53e-04 2.82e-03 1.86e-03 0.0 *** Restarting incremental Fock matrix formation *** 7 -76.1874720920177850 8.05e-05 6.71e-04 4.31e-03 9.99e-04 0.0 8 -76.1874821592127347 -1.01e-05 3.43e-04 1.75e-03 7.97e-04 0.1 9 -76.1874827442788956 -5.85e-07 1.86e-04 1.04e-03 8.10e-04 0.0 10 -76.1874849600490620 -2.22e-06 7.42e-06 4.37e-05 6.63e-05 0.0 11 -76.1874849699121057 -9.86e-09 1.69e-06 1.03e-05 2.18e-05 0.0 **** Energy Check signals convergence **** ***************************************************** * SUCCESS * * SCF CONVERGED AFTER 11 CYCLES * ***************************************************** Recomputing exchange energy using gridx3 ... done ( 0.056 sec) Old exchange energy : -1.749132205 Eh New exchange energy : -1.749145766 Eh Exchange energy change after final integration : -0.000013561 Eh Total energy after final integration : -76.187498532 Eh **** ENERGY FILE WAS UPDATED (water_opt_2.en.tmp) **** ---------------- TOTAL SCF ENERGY ---------------- Total Energy : -76.18749853158856 Eh -2073.16723 eV Components: Nuclear Repulsion : 7.18018627542602 Eh 195.38280 eV Electronic Energy : -83.36767124617117 Eh -2268.54967 eV One Electron Energy: -119.67634332942501 Eh -3256.55886 eV Two Electron Energy: 36.30867208325385 Eh 988.00920 eV Virial components: Potential Energy : -151.39952128223655 Eh -4119.79042 eV Kinetic Energy : 75.21202275064799 Eh 2046.62319 eV Virial Ratio : 2.01296967885274 DFT components: N(Alpha) : 4.999999805614 electrons N(Beta) : 4.999999805614 electrons N(Total) : 9.999999611229 electrons E(X) : -6.989838921338 Eh E(C) : -0.395420201490 Eh E(XC) : -7.385259122829 Eh --------------- SCF CONVERGENCE --------------- Last Energy change ... 9.8630e-09 Tolerance : 1.0000e-08 Last MAX-Density change ... 1.0303e-05 Tolerance : 1.0000e-07 Last RMS-Density change ... 1.6913e-06 Tolerance : 5.0000e-09 Last DIIS Error ... 1.8555e-03 Tolerance : 5.0000e-07 Last Orbital Gradient ... 2.1791e-05 Tolerance : 1.0000e-05 Last Orbital Rotation ... 6.6745e-06 Tolerance : 1.0000e-05 ---------------- ORBITAL ENERGIES ---------------- NO OCC E(Eh) E(eV) 0 2.0000 -19.086493 -519.3699 1 2.0000 -0.852474 -23.1970 2 2.0000 -0.460733 -12.5372 3 2.0000 -0.243817 -6.6346 4 2.0000 -0.237977 -6.4757 5 0.0000 -0.063325 -1.7232 6 0.0000 0.079364 2.1596 7 0.0000 0.384124 10.4525 8 0.0000 0.543280 14.7834 9 0.0000 0.935752 25.4631 10 0.0000 0.936380 25.4802 11 0.0000 1.075562 29.2675 12 0.0000 1.222706 33.2715 13 0.0000 1.301825 35.4245 14 0.0000 1.427995 38.8577 15 0.0000 1.576544 42.8999 *Only the first 10 virtual orbitals were printed. ******************************** * MULLIKEN POPULATION ANALYSIS * ******************************** ----------------------- MULLIKEN ATOMIC CHARGES ----------------------- 0 O : -0.619409 1 H : 0.309704 2 H : 0.309704 Sum of atomic charges: 0.0000000 -------------------------------- MULLIKEN REDUCED ORBITAL CHARGES -------------------------------- 0 O s : 3.771104 s : 3.771104 pz : 1.982087 p : 4.846172 px : 1.007648 py : 1.856436 dz2 : 0.000701 d : 0.002133 dxz : 0.000000 dyz : 0.000183 dx2y2 : 0.000577 dxy : 0.000672 1 H s : 0.650752 s : 0.650752 pz : 0.008865 p : 0.039544 px : 0.022228 py : 0.008450 2 H s : 0.650752 s : 0.650752 pz : 0.008865 p : 0.039544 px : 0.022228 py : 0.008450 ******************************* * LOEWDIN POPULATION ANALYSIS * ******************************* ---------------------- LOEWDIN ATOMIC CHARGES ---------------------- 0 O : -0.487781 1 H : 0.243890 2 H : 0.243890 ------------------------------- LOEWDIN REDUCED ORBITAL CHARGES ------------------------------- 0 O s : 3.578189 s : 3.578189 pz : 1.961660 p : 4.907132 px : 1.100529 py : 1.844943 dz2 : 0.000707 d : 0.002460 dxz : 0.000000 dyz : 0.000153 dx2y2 : 0.000548 dxy : 0.001052 1 H s : 0.666053 s : 0.666053 pz : 0.019094 p : 0.090057 px : 0.052270 py : 0.018693 2 H s : 0.666053 s : 0.666053 pz : 0.019094 p : 0.090057 px : 0.052270 py : 0.018693 ***************************** * 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 O 8.6194 8.0000 -0.6194 1.6422 1.6422 -0.0000 1 H 0.6903 1.0000 0.3097 0.9152 0.9152 0.0000 2 H 0.6903 1.0000 0.3097 0.9152 0.9152 0.0000 Mayer bond orders larger than 0.100000 B( 0-O , 1-H ) : 0.8211 B( 0-O , 2-H ) : 0.8211 ------- TIMINGS ------- Total SCF time: 0 days 0 hours 0 min 0 sec Total time .... 0.637 sec Sum of individual times .... 0.579 sec ( 90.9%) SCF preparation .... 0.038 sec ( 6.0%) Fock matrix formation .... 0.535 sec ( 84.0%) Startup .... 0.000 sec ( 0.1% of F) Split-RI-J .... 0.017 sec ( 3.1% of F) Chain of spheres X .... 0.378 sec ( 70.7% of F) XC integration .... 0.181 sec ( 33.9% of F) XC Preparation .... 0.000 sec ( 0.0% of XC) Basis function eval. .... 0.075 sec ( 41.2% of XC) Density eval. .... 0.021 sec ( 11.4% of XC) XC-Functional eval. .... 0.051 sec ( 28.2% of XC) XC-Potential eval. .... 0.020 sec ( 11.0% of XC) Diagonalization .... 0.000 sec ( 0.0%) Density matrix formation .... 0.001 sec ( 0.2%) Total Energy calculation .... 0.000 sec ( 0.1%) Population analysis .... 0.001 sec ( 0.1%) Orbital Transformation .... 0.000 sec ( 0.1%) Orbital Orthonormalization .... 0.000 sec ( 0.0%) DIIS solution .... 0.002 sec ( 0.3%) SOSCF solution .... 0.001 sec ( 0.2%) Finished LeanSCF after 0.6 sec Maximum memory used throughout the entire LEANSCF-calculation: 5.0 MB ------------------------- -------------------- FINAL SINGLE POINT ENERGY -76.187498531589 ------------------------- -------------------- ------------------------------------------------------------------------------ ORCA SCF GRADIENT CALCULATION ------------------------------------------------------------------------------ Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) done ( 0.2 sec) XC gradient ... done ( 0.1 sec) ------------------ CARTESIAN GRADIENT ------------------ 1 O : -0.000000003 -0.020678315 -0.000000000 2 H : 0.129211896 0.010339153 0.000000001 3 H : -0.129211893 0.010339163 -0.000000000 Difference to translation invariance: : 0.0000000000 0.0000000000 -0.0000000000 Difference to rotation invariance: : -0.0000000001 -0.0000000026 -0.0000000212 Norm of the Cartesian gradient ... 0.1844798538 RMS gradient ... 0.0614932846 MAX gradient ... 0.1292118959 ------- TIMINGS ------- Total SCF gradient time .... 0.334 sec Densities .... 0.000 sec ( 0.0%) One electron gradient .... 0.003 sec ( 0.9%) RI-J Coulomb gradient .... 0.053 sec ( 15.9%) COSX gradient .... 0.223 sec ( 66.7%) XC gradient .... 0.055 sec ( 16.4%) Maximum memory used throughout the entire SCFGRAD-calculation: 6.2 MB ------------------------------------------------------------------------------ ORCA GEOMETRY RELAXATION STEP ------------------------------------------------------------------------------ Reading the OPT-File .... done Getting information on internals .... done Copying old internal coords+grads .... done Making the new internal coordinates .... (2022 redundants) done Validating the new internal coordinates .... (2022 redundants) done Calculating the B-matrix .... done Calculating the G,G- and P matrices .... done Transforming gradient to internals .... done Projecting the internal gradient .... done Number of atoms .... 3 Number of internal coordinates .... 3 Current Energy .... -76.187498532 Eh Current gradient norm .... 0.184479854 Eh/bohr Maximum allowed component of the step .... 0.300 Current trust radius .... 0.300 Evaluating the initial hessian .... (Almloef) done Projecting the Hessian .... done Forming the augmented Hessian .... done Diagonalizing the augmented Hessian .... done Last element of RFO vector .... 0.858763067 Lowest eigenvalues of augmented Hessian: -0.114453796 0.202606599 0.234167704 Length of the computed step .... 0.596640592 Warning: the length of the step is outside the trust region - taking restricted step instead The input lambda is .... 0.201607 iter: 5 x= 0.195004 g=486818.062721 f(x)= 1235.330441 iter: 10 x= 0.143903 g= 1095.063139 f(x)= 21.657558 iter: 15 x= -0.200664 g= 2.952784 f(x)= 0.340773 iter: 20 x= -0.432253 g= 0.281467 f(x)= 0.000002 The output lambda is .... -0.432253 (22 iterations) The final length of the internal step .... 0.300000000 Converting the step to Cartesian space: Initial RMS(Int)= 0.1732050808 Transforming coordinates: Iter 0: RMS(Cart)= 0.1045268965 RMS(Int)= 0.1726278364 Iter 5: RMS(Cart)= 0.0000000285 RMS(Int)= 0.0000000482 done Storing new coordinates .... done .--------------------. ----------------------|Geometry convergence|------------------------- Item value Tolerance Converged --------------------------------------------------------------------- RMS gradient 0.1108342547 0.0001000000 NO MAX gradient 0.1257540823 0.0003000000 NO RMS step 0.1732050808 0.0020000000 NO MAX step 0.1980816919 0.0040000000 NO ------------------------------------------------------------------------- ........................................................ Max(Bonds) 0.1048 Max(Angles) 6.15 Max(Dihed) 0.00 Max(Improp) 0.00 --------------------------------------------------------------------- The optimization has not yet converged - more geometry cycles are needed --------------------------------------------------------------------------- Redundant Internal Coordinates (Angstroem and degrees) Definition Value dE/dq Step New-Value ---------------------------------------------------------------------------- 1. B(H 1,O 0) 1.2166 0.125754 -0.1048 1.1117 2. B(H 2,O 0) 1.2166 0.125754 -0.1048 1.1117 3. A(H 1,O 0,H 2) 161.08 0.072281 -6.15 154.92 ---------------------------------------------------------------------------- Geometry step timings: Preparation and reading OPT file: 0.000 s ( 4.658 %) Internal coordinates : 0.000 s ( 3.014 %) B/P matrices and projection : 0.000 s (21.644 %) Hessian update/contruction : 0.000 s (17.260 %) Making the step : 0.000 s (22.740 %) Converting the step to Cartesian: 0.000 s ( 4.932 %) Storing new data : 0.000 s ( 4.932 %) Checking convergence : 0.000 s ( 4.658 %) Final printing : 0.000 s (16.164 %) Total time : 0.000 s Time for energy+gradient : 1.190 s Time for complete geometry iter : 1.205 s ************************************************************* * GEOMETRY OPTIMIZATION CYCLE 2 * ************************************************************* --------------------------------- CARTESIAN COORDINATES (ANGSTROEM) --------------------------------- O 0.000000 0.227563 0.000000 H 1.085219 -0.013782 0.000000 H -1.085219 -0.013782 0.000000 ---------------------------- CARTESIAN COORDINATES (A.U.) ---------------------------- NO LB ZA FRAG MASS X Y Z 0 O 8.0000 0 15.999 0.000000 0.430032 0.000000 1 H 1.0000 0 1.008 2.050767 -0.026043 0.000000 2 H 1.0000 0 1.008 -2.050767 -0.026043 0.000000 -------------------------------- INTERNAL COORDINATES (ANGSTROEM) -------------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 H 1 0 0 1.111732189836 0.00000000 0.00000000 H 1 2 0 1.111732192617 154.92378182 0.00000000 --------------------------- INTERNAL COORDINATES (A.U.) --------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 H 1 0 0 2.100869373054 0.00000000 0.00000000 H 1 2 0 2.100869378310 154.92378182 0.00000000 ------------------------------------------------------------------------------ ___ / \ - 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 ... 3 Number of basis functions ... 24 Number of shells ... 12 Maximum angular momentum ... 2 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 ... 71 # of shells in Aux-J ... 25 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 = 12 => 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 ... 78 Shell pairs after pre-screening ... 78 Total number of primitive shell pairs ... 272 Primitive shell pairs kept ... 259 la=0 lb=0: 28 shell pairs la=1 lb=0: 28 shell pairs la=1 lb=1: 10 shell pairs la=2 lb=0: 7 shell pairs la=2 lb=1: 4 shell pairs la=2 lb=2: 1 shell pairs Checking whether 4 symmetric matrices of dimension 24 fit in memory :Max Core in MB = 4096.00 MB in use = 3.23 MB left = 4092.77 MB needed = 0.01 Data fit in memory = YES Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 7.859705886811 Eh Diagonalization of the overlap matrix: Smallest eigenvalue ... 6.417e-02 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 ... 0.000 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 ... 12760 Total number of batches ... 200 Average number of points per batch ... 63 Average number of grid points per atom ... 4253 -------------------- 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 ... 1664 Total number of batches ... 14 Average number of points per batch ... 118 Average number of grid points per atom ... 555 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 ... 3522 Total number of batches ... 30 Average number of points per batch ... 117 Average number of grid points per atom ... 1174 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 ... 7788 Total number of batches ... 62 Average number of points per batch ... 125 Average number of grid points per atom ... 2596 UseSFitting ... on Grids setup in 0.1 sec Initializing property integral containers ... done ( 0.0 sec) SHARK setup successfully completed in 0.1 seconds Maximum memory used throughout the entire STARTUP-calculation: 8.8 MB Occupation numbers will be reassigned to an Aufbau configuration **** ENERGY FILE WAS UPDATED (water_opt_2.en.tmp) **** Finished Guess after 0.0 sec Maximum memory used throughout the entire GUESS-calculation: 5.5 MB ----------------------------------------D-I-I-S-------------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) ------------------------------------------------------------------------------------------- *** Starting incremental Fock matrix formation *** 1 -76.2382832745337140 0.00e+00 1.86e-03 1.15e-02 5.09e-02 0.700 0.1 2 -76.2394546402417177 -1.17e-03 1.46e-03 8.52e-03 3.14e-02 0.700 0.0 ***Turning on AO-DIIS*** 3 -76.2402090668491468 -7.54e-04 1.02e-03 6.66e-03 1.84e-02 0.700 0.0 4 -76.2407250666658882 -5.16e-04 2.39e-03 1.48e-02 1.50e-02 0.000 0.0 *** Initializing SOSCF *** ---------------------------------------S-O-S-C-F-------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) -------------------------------------------------------------------------------------- 5 -76.2419560585872631 -1.23e-03 2.14e-04 1.52e-03 2.88e-03 0.0 *** Restarting incremental Fock matrix formation *** 6 -76.2419727355927250 -1.67e-05 9.48e-05 6.00e-04 2.59e-04 0.1 7 -76.2419729577747631 -2.22e-07 5.93e-05 3.55e-04 2.36e-04 0.0 8 -76.2419731225042767 -1.65e-07 2.30e-05 1.54e-04 5.55e-05 0.0 9 -76.2419731384940036 -1.60e-08 2.38e-06 1.55e-05 9.07e-06 0.0 10 -76.2419731392628393 -7.69e-10 2.47e-07 1.25e-06 2.35e-06 0.0 **** Energy Check signals convergence **** ***************************************************** * SUCCESS * * SCF CONVERGED AFTER 10 CYCLES * ***************************************************** Recomputing exchange energy using gridx3 ... done ( 0.056 sec) Old exchange energy : -1.763778728 Eh New exchange energy : -1.763801526 Eh Exchange energy change after final integration : -0.000022798 Eh Total energy after final integration : -76.241995937 Eh **** ENERGY FILE WAS UPDATED (water_opt_2.en.tmp) **** ---------------- TOTAL SCF ENERGY ---------------- Total Energy : -76.24199593722842 Eh -2074.65018 eV Components: Nuclear Repulsion : 7.85970588681088 Eh 213.87347 eV Electronic Energy : -84.10167902619155 Eh -2288.52303 eV One Electron Energy: -120.91479688510022 Eh -3290.25890 eV Two Electron Energy: 36.81311785890867 Eh 1001.73586 eV Virial components: Potential Energy : -151.59687618849580 Eh -4125.16072 eV Kinetic Energy : 75.35488025126736 Eh 2050.51054 eV Virial Ratio : 2.01177250475355 DFT components: N(Alpha) : 4.999999071139 electrons N(Beta) : 4.999999071139 electrons N(Total) : 9.999998142278 electrons E(X) : -7.035742912515 Eh E(C) : -0.398398677856 Eh E(XC) : -7.434141590371 Eh --------------- SCF CONVERGENCE --------------- Last Energy change ... 7.6884e-10 Tolerance : 1.0000e-08 Last MAX-Density change ... 1.2532e-06 Tolerance : 1.0000e-07 Last RMS-Density change ... 2.4659e-07 Tolerance : 5.0000e-09 Last DIIS Error ... 2.8802e-03 Tolerance : 5.0000e-07 Last Orbital Gradient ... 2.3550e-06 Tolerance : 1.0000e-05 Last Orbital Rotation ... 8.4357e-07 Tolerance : 1.0000e-05 Total SCF time: 0 days 0 hours 0 min 0 sec Finished LeanSCF after 0.6 sec Maximum memory used throughout the entire LEANSCF-calculation: 5.0 MB ------------------------- -------------------- FINAL SINGLE POINT ENERGY -76.241995937228 ------------------------- -------------------- ------------------------------------------------------------------------------ ORCA SCF GRADIENT CALCULATION ------------------------------------------------------------------------------ Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) done ( 0.2 sec) XC gradient ... done ( 0.1 sec) ------------------ CARTESIAN GRADIENT ------------------ 1 O : -0.000000022 -0.016239215 -0.000000010 2 H : 0.111658160 0.008119607 0.000000006 3 H : -0.111658139 0.008119608 0.000000004 Difference to translation invariance: : -0.0000000000 0.0000000000 0.0000000000 Difference to rotation invariance: : -0.0000000047 -0.0000000053 0.0000000071 Norm of the Cartesian gradient ... 0.1591560646 RMS gradient ... 0.0530520215 MAX gradient ... 0.1116581605 ------- TIMINGS ------- Total SCF gradient time .... 0.341 sec Densities .... 0.000 sec ( 0.0%) One electron gradient .... 0.003 sec ( 0.9%) RI-J Coulomb gradient .... 0.054 sec ( 15.9%) COSX gradient .... 0.227 sec ( 66.7%) XC gradient .... 0.056 sec ( 16.5%) Maximum memory used throughout the entire SCFGRAD-calculation: 6.3 MB ------------------------------------------------------------------------------ ORCA GEOMETRY RELAXATION STEP ------------------------------------------------------------------------------ Reading the OPT-File .... done Getting information on internals .... done Copying old internal coords+grads .... done Making the new internal coordinates .... (2022 redundants) done Validating the new internal coordinates .... (2022 redundants) done Calculating the B-matrix .... done Calculating the G,G- and P matrices .... done Transforming gradient to internals .... done Projecting the internal gradient .... done Number of atoms .... 3 Number of internal coordinates .... 3 Current Energy .... -76.241995937 Eh Current gradient norm .... 0.159156065 Eh/bohr Maximum allowed component of the step .... 0.300 Current trust radius .... 0.300 Updating the Hessian (BFGS) .... done Forming the augmented Hessian .... done Diagonalizing the augmented Hessian .... done Last element of RFO vector .... 0.790383276 Lowest eigenvalues of augmented Hessian: -0.128648841 0.202606599 0.212724580 Length of the computed step .... 0.775083030 Warning: the length of the step is outside the trust region - taking restricted step instead The input lambda is .... 0.084340 iter: 5 x= 0.077747 g=423644.821998 f(x)= 1072.240544 iter: 10 x= 0.027838 g= 971.070648 f(x)= 18.553960 iter: 15 x= -0.289495 g= 2.741313 f(x)= 0.282624 iter: 20 x= -0.467751 g= 0.325315 f(x)= 0.000000 The output lambda is .... -0.467751 (22 iterations) The final length of the internal step .... 0.300000000 Converting the step to Cartesian space: Initial RMS(Int)= 0.1732050808 Transforming coordinates: Iter 0: RMS(Cart)= 0.1048507141 RMS(Int)= 0.1730289513 Iter 5: RMS(Cart)= 0.0000000526 RMS(Int)= 0.0000001190 done Storing new coordinates .... done The predicted energy change is .... -0.045950728 Previously predicted energy change .... -0.048241193 Actually observed energy change .... -0.054497406 Ratio of predicted to observed change .... 1.129686101 New trust radius .... 0.450000000 .--------------------. ----------------------|Geometry convergence|------------------------- Item value Tolerance Converged --------------------------------------------------------------------- Energy change -0.0544974056 0.0000050000 NO RMS gradient 0.0958543790 0.0001000000 NO MAX gradient 0.1072326413 0.0003000000 NO RMS step 0.1732050808 0.0020000000 NO MAX step 0.1927168244 0.0040000000 NO ------------------------------------------------------------------------- ........................................................ Max(Bonds) 0.1020 Max(Angles) 7.18 Max(Dihed) 0.00 Max(Improp) 0.00 --------------------------------------------------------------------- The optimization has not yet converged - more geometry cycles are needed --------------------------------------------------------------------------- Redundant Internal Coordinates (Angstroem and degrees) Definition Value dE/dq Step New-Value ---------------------------------------------------------------------------- 1. B(H 1,O 0) 1.1117 0.107233 -0.1020 1.0098 2. B(H 2,O 0) 1.1117 0.107233 -0.1020 1.0098 3. A(H 1,O 0,H 2) 154.92 0.067576 -7.18 147.74 ---------------------------------------------------------------------------- Geometry step timings: Preparation and reading OPT file: 0.000 s ( 3.927 %) Internal coordinates : 0.000 s ( 2.618 %) B/P matrices and projection : 0.000 s (18.063 %) Hessian update/contruction : 0.000 s (33.770 %) Making the step : 0.000 s (13.351 %) Converting the step to Cartesian: 0.000 s ( 4.188 %) Storing new data : 0.000 s ( 4.712 %) Checking convergence : 0.000 s ( 6.021 %) Final printing : 0.000 s (13.089 %) Total time : 0.000 s Time for energy+gradient : 1.142 s Time for complete geometry iter : 1.157 s ************************************************************* * GEOMETRY OPTIMIZATION CYCLE 3 * ************************************************************* --------------------------------- CARTESIAN COORDINATES (ANGSTROEM) --------------------------------- O 0.000000 0.253685 0.000000 H 0.970001 -0.026842 0.000000 H -0.970001 -0.026842 0.000000 ---------------------------- CARTESIAN COORDINATES (A.U.) ---------------------------- NO LB ZA FRAG MASS X Y Z 0 O 8.0000 0 15.999 0.000000 0.479395 0.000000 1 H 1.0000 0 1.008 1.833036 -0.050725 0.000000 2 H 1.0000 0 1.008 -1.833036 -0.050725 0.000000 -------------------------------- INTERNAL COORDINATES (ANGSTROEM) -------------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 H 1 0 0 1.009750844983 0.00000000 0.00000000 H 1 2 0 1.009750880616 147.73996051 0.00000000 --------------------------- INTERNAL COORDINATES (A.U.) --------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 H 1 0 0 1.908152560514 0.00000000 0.00000000 H 1 2 0 1.908152627850 147.73996051 0.00000000 ------------------------------------------------------------------------------ ___ / \ - 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 ... 3 Number of basis functions ... 24 Number of shells ... 12 Maximum angular momentum ... 2 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 ... 71 # of shells in Aux-J ... 25 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 = 12 => 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 ... 78 Shell pairs after pre-screening ... 78 Total number of primitive shell pairs ... 272 Primitive shell pairs kept ... 263 la=0 lb=0: 28 shell pairs la=1 lb=0: 28 shell pairs la=1 lb=1: 10 shell pairs la=2 lb=0: 7 shell pairs la=2 lb=1: 4 shell pairs la=2 lb=2: 1 shell pairs Checking whether 4 symmetric matrices of dimension 24 fit in memory :Max Core in MB = 4096.00 MB in use = 3.23 MB left = 4092.77 MB needed = 0.01 Data fit in memory = YES Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 8.657845181063 Eh Diagonalization of the overlap matrix: Smallest eigenvalue ... 5.314e-02 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 ... 0.000 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 ... 12740 Total number of batches ... 200 Average number of points per batch ... 63 Average number of grid points per atom ... 4247 -------------------- 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 ... 1664 Total number of batches ... 14 Average number of points per batch ... 118 Average number of grid points per atom ... 555 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 ... 3522 Total number of batches ... 29 Average number of points per batch ... 121 Average number of grid points per atom ... 1174 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 ... 7780 Total number of batches ... 63 Average number of points per batch ... 123 Average number of grid points per atom ... 2593 UseSFitting ... on Grids setup in 0.1 sec Initializing property integral containers ... done ( 0.0 sec) SHARK setup successfully completed in 0.1 seconds Maximum memory used throughout the entire STARTUP-calculation: 8.8 MB Occupation numbers will be reassigned to an Aufbau configuration **** ENERGY FILE WAS UPDATED (water_opt_2.en.tmp) **** Finished Guess after 0.0 sec Maximum memory used throughout the entire GUESS-calculation: 5.5 MB ----------------------------------------D-I-I-S-------------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) ------------------------------------------------------------------------------------------- *** Starting incremental Fock matrix formation *** 1 -76.2785073494276702 0.00e+00 2.14e-03 1.14e-02 5.18e-02 0.700 0.1 2 -76.2799239238465958 -1.42e-03 1.69e-03 1.01e-02 3.19e-02 0.700 0.0 ***Turning on AO-DIIS*** 3 -76.2808435236032096 -9.20e-04 1.17e-03 8.22e-03 1.87e-02 0.700 0.0 4 -76.2814655152408534 -6.22e-04 2.71e-03 1.81e-02 1.53e-02 0.000 0.0 *** Initializing SOSCF *** ---------------------------------------S-O-S-C-F-------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) -------------------------------------------------------------------------------------- 5 -76.2829384045467549 -1.47e-03 2.08e-04 1.45e-03 2.70e-03 0.0 *** Restarting incremental Fock matrix formation *** 6 -76.2829536920834244 -1.53e-05 9.13e-05 6.78e-04 3.31e-04 0.1 7 -76.2829536369437164 5.51e-08 4.83e-05 3.41e-04 3.63e-04 0.0 8 -76.2829540219760531 -3.85e-07 2.05e-06 1.34e-05 1.22e-05 0.0 9 -76.2829540218420021 1.34e-10 5.93e-07 4.17e-06 3.39e-06 0.0 **** Energy Check signals convergence **** ***************************************************** * SUCCESS * * SCF CONVERGED AFTER 9 CYCLES * ***************************************************** Recomputing exchange energy using gridx3 ... done ( 0.056 sec) Old exchange energy : -1.780923227 Eh New exchange energy : -1.780939009 Eh Exchange energy change after final integration : -0.000015782 Eh Total energy after final integration : -76.282969804 Eh **** ENERGY FILE WAS UPDATED (water_opt_2.en.tmp) **** ---------------- TOTAL SCF ENERGY ---------------- Total Energy : -76.28296980398225 Eh -2075.76514 eV Components: Nuclear Repulsion : 8.65784518106281 Eh 235.59194 eV Electronic Energy : -84.94079920317051 Eh -2311.35665 eV One Electron Energy: -122.32045290743886 Eh -3328.50874 eV Two Electron Energy: 37.37965370426834 Eh 1017.15209 eV Virial components: Potential Energy : -151.86340214796951 Eh -4132.41326 eV Kinetic Energy : 75.58043234398727 Eh 2056.64812 eV Virial Ratio : 2.00929522944242 DFT components: N(Alpha) : 5.000000028599 electrons N(Beta) : 5.000000028599 electrons N(Total) : 10.000000057197 electrons E(X) : -7.091793158783 Eh E(C) : -0.401483888695 Eh E(XC) : -7.493277047479 Eh --------------- SCF CONVERGENCE --------------- Last Energy change ... -1.3405e-10 Tolerance : 1.0000e-08 Last MAX-Density change ... 4.1717e-06 Tolerance : 1.0000e-07 Last RMS-Density change ... 5.9299e-07 Tolerance : 5.0000e-09 Last DIIS Error ... 2.6978e-03 Tolerance : 5.0000e-07 Last Orbital Gradient ... 3.3919e-06 Tolerance : 1.0000e-05 Last Orbital Rotation ... 3.8085e-06 Tolerance : 1.0000e-05 Total SCF time: 0 days 0 hours 0 min 0 sec Finished LeanSCF after 0.6 sec Maximum memory used throughout the entire LEANSCF-calculation: 5.1 MB ------------------------- -------------------- FINAL SINGLE POINT ENERGY -76.282969803982 ------------------------- -------------------- ------------------------------------------------------------------------------ ORCA SCF GRADIENT CALCULATION ------------------------------------------------------------------------------ Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) done ( 0.2 sec) XC gradient ... done ( 0.1 sec) ------------------ CARTESIAN GRADIENT ------------------ 1 O : 0.000000030 -0.030565934 0.000000000 2 H : 0.062969602 0.015282972 0.000000002 3 H : -0.062969632 0.015282961 -0.000000002 Difference to translation invariance: : 0.0000000000 0.0000000000 0.0000000000 Difference to rotation invariance: : 0.0000000001 -0.0000000060 0.0000000025 Norm of the Cartesian gradient ... 0.0966010338 RMS gradient ... 0.0322003446 MAX gradient ... 0.0629696317 ------- TIMINGS ------- Total SCF gradient time .... 0.334 sec Densities .... 0.000 sec ( 0.0%) One electron gradient .... 0.003 sec ( 0.9%) RI-J Coulomb gradient .... 0.053 sec ( 15.9%) COSX gradient .... 0.225 sec ( 67.2%) XC gradient .... 0.053 sec ( 15.9%) Maximum memory used throughout the entire SCFGRAD-calculation: 6.2 MB ------------------------------------------------------------------------------ ORCA GEOMETRY RELAXATION STEP ------------------------------------------------------------------------------ Reading the OPT-File .... done Getting information on internals .... done Copying old internal coords+grads .... done Making the new internal coordinates .... (2022 redundants) done Validating the new internal coordinates .... (2022 redundants) done Calculating the B-matrix .... done Calculating the G,G- and P matrices .... done Transforming gradient to internals .... done Projecting the internal gradient .... done Number of atoms .... 3 Number of internal coordinates .... 3 Current Energy .... -76.282969804 Eh Current gradient norm .... 0.096601034 Eh/bohr Maximum allowed component of the step .... 0.300 Current trust radius .... 0.450 Updating the Hessian (BFGS) .... done Forming the augmented Hessian .... done Diagonalizing the augmented Hessian .... done Last element of RFO vector .... 0.911228541 Lowest eigenvalues of augmented Hessian: -0.044659093 0.202065895 0.202606599 Length of the computed step .... 0.452028353 Warning: the length of the step is outside the trust region - taking restricted step instead The input lambda is .... 0.162538 iter: 5 x= 0.155946 g=128183.991201 f(x)= 324.283527 iter: 10 x= 0.106863 g= 299.633974 f(x)= 5.548253 iter: 15 x= -0.043747 g= 2.400751 f(x)= 0.035131 The output lambda is .... -0.045624 (19 iterations) The final length of the internal step .... 0.424476982 Converting the step to Cartesian space: Initial RMS(Int)= 0.2450718996 Transforming coordinates: Iter 0: RMS(Cart)= 0.1459990894 RMS(Int)= 0.2468408417 Iter 5: RMS(Cart)= 0.0000068867 RMS(Int)= 0.0000121637 done Storing new coordinates .... done The predicted energy change is .... -0.026190354 Previously predicted energy change .... -0.045950728 Actually observed energy change .... -0.040973867 Ratio of predicted to observed change .... 0.891691359 New trust radius .... 0.675000000 .--------------------. ----------------------|Geometry convergence|------------------------- Item value Tolerance Converged --------------------------------------------------------------------- Energy change -0.0409738668 0.0000050000 NO RMS gradient 0.0580126134 0.0001000000 NO MAX gradient 0.0613956243 0.0003000000 NO RMS step 0.2450718996 0.0020000000 NO MAX step 0.3000000000 0.0040000000 NO ------------------------------------------------------------------------- ........................................................ Max(Bonds) 0.1124 Max(Angles) 17.19 Max(Dihed) 0.00 Max(Improp) 0.00 --------------------------------------------------------------------- The optimization has not yet converged - more geometry cycles are needed --------------------------------------------------------------------------- Redundant Internal Coordinates (Angstroem and degrees) Definition Value dE/dq Step New-Value ---------------------------------------------------------------------------- 1. B(H 1,O 0) 1.0098 0.056245 -0.1124 0.8974 2. B(H 2,O 0) 1.0098 0.056245 -0.1124 0.8974 3. A(H 1,O 0,H 2) 147.74 0.061396 -17.19 130.55 ---------------------------------------------------------------------------- Geometry step timings: Preparation and reading OPT file: 0.000 s ( 4.348 %) Internal coordinates : 0.000 s ( 2.899 %) B/P matrices and projection : 0.000 s (20.000 %) Hessian update/contruction : 0.000 s (29.275 %) Making the step : 0.000 s (13.623 %) Converting the step to Cartesian: 0.000 s ( 4.638 %) Storing new data : 0.000 s ( 4.928 %) Checking convergence : 0.000 s ( 6.377 %) Final printing : 0.000 s (13.333 %) Total time : 0.000 s Time for energy+gradient : 1.086 s Time for complete geometry iter : 1.101 s ************************************************************* * GEOMETRY OPTIMIZATION CYCLE 4 * ************************************************************* --------------------------------- CARTESIAN COORDINATES (ANGSTROEM) --------------------------------- O -0.000000 0.316889 0.000000 H 0.815120 -0.058445 0.000000 H -0.815120 -0.058445 0.000000 ---------------------------- CARTESIAN COORDINATES (A.U.) ---------------------------- NO LB ZA FRAG MASS X Y Z 0 O 8.0000 0 15.999 -0.000000 0.598834 0.000000 1 H 1.0000 0 1.008 1.540353 -0.110444 0.000000 2 H 1.0000 0 1.008 -1.540353 -0.110444 0.000000 -------------------------------- INTERNAL COORDINATES (ANGSTROEM) -------------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 H 1 0 0 0.897382844875 0.00000000 0.00000000 H 1 2 0 0.897382712069 130.55122711 0.00000000 --------------------------- INTERNAL COORDINATES (A.U.) --------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 H 1 0 0 1.695807814092 0.00000000 0.00000000 H 1 2 0 1.695807563126 130.55122711 0.00000000 ------------------------------------------------------------------------------ ___ / \ - 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 ... 3 Number of basis functions ... 24 Number of shells ... 12 Maximum angular momentum ... 2 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 ... 71 # of shells in Aux-J ... 25 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 = 12 => 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 ... 78 Shell pairs after pre-screening ... 78 Total number of primitive shell pairs ... 272 Primitive shell pairs kept ... 265 la=0 lb=0: 28 shell pairs la=1 lb=0: 28 shell pairs la=1 lb=1: 10 shell pairs la=2 lb=0: 7 shell pairs la=2 lb=1: 4 shell pairs la=2 lb=2: 1 shell pairs Checking whether 4 symmetric matrices of dimension 24 fit in memory :Max Core in MB = 4096.00 MB in use = 3.23 MB left = 4092.77 MB needed = 0.01 Data fit in memory = YES Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 9.759632947004 Eh Diagonalization of the overlap matrix: Smallest eigenvalue ... 3.853e-02 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 ... 0.000 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 ... 12744 Total number of batches ... 201 Average number of points per batch ... 63 Average number of grid points per atom ... 4248 -------------------- 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 ... 1662 Total number of batches ... 15 Average number of points per batch ... 110 Average number of grid points per atom ... 554 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 ... 3514 Total number of batches ... 29 Average number of points per batch ... 121 Average number of grid points per atom ... 1171 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 ... 7748 Total number of batches ... 62 Average number of points per batch ... 124 Average number of grid points per atom ... 2583 UseSFitting ... on Grids setup in 0.1 sec Initializing property integral containers ... done ( 0.0 sec) SHARK setup successfully completed in 0.1 seconds Maximum memory used throughout the entire STARTUP-calculation: 8.8 MB Occupation numbers will be reassigned to an Aufbau configuration **** ENERGY FILE WAS UPDATED (water_opt_2.en.tmp) **** Finished Guess after 0.0 sec Maximum memory used throughout the entire GUESS-calculation: 5.5 MB ----------------------------------------D-I-I-S-------------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) ------------------------------------------------------------------------------------------- *** Starting incremental Fock matrix formation *** 1 -76.2892929149658983 0.00e+00 3.40e-03 1.84e-02 5.14e-02 0.700 0.1 2 -76.2924830872431841 -3.19e-03 2.74e-03 1.40e-02 3.39e-02 0.700 0.0 ***Turning on AO-DIIS*** 3 -76.2946079194381923 -2.12e-03 1.95e-03 1.11e-02 2.41e-02 0.700 0.0 4 -76.2960497011937804 -1.44e-03 4.58e-03 2.55e-02 1.72e-02 0.000 0.0 *** Initializing SOSCF *** ---------------------------------------S-O-S-C-F-------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) -------------------------------------------------------------------------------------- 5 -76.2994744143213666 -3.42e-03 2.82e-04 1.98e-03 3.14e-03 0.0 *** Restarting incremental Fock matrix formation *** 6 -76.2994945585330271 -2.01e-05 1.63e-04 1.19e-03 5.76e-04 0.1 7 -76.2994939583140450 6.00e-07 8.86e-05 6.35e-04 7.14e-04 0.0 8 -76.2994954156891083 -1.46e-06 1.09e-06 6.26e-06 5.00e-06 0.0 9 -76.2994954154399068 2.49e-10 1.37e-07 6.05e-07 1.59e-06 0.0 **** Energy Check signals convergence **** ***************************************************** * SUCCESS * * SCF CONVERGED AFTER 9 CYCLES * ***************************************************** Recomputing exchange energy using gridx3 ... done ( 0.056 sec) Old exchange energy : -1.804557518 Eh New exchange energy : -1.804518187 Eh Exchange energy change after final integration : 0.000039331 Eh Total energy after final integration : -76.299456084 Eh **** ENERGY FILE WAS UPDATED (water_opt_2.en.tmp) **** ---------------- TOTAL SCF ENERGY ---------------- Total Energy : -76.29945608436945 Eh -2076.21375 eV Components: Nuclear Repulsion : 9.75963294700392 Eh 265.57311 eV Electronic Energy : -86.05912836242365 Eh -2341.78794 eV One Electron Energy: -124.17269763473290 Eh -3378.91088 eV Two Electron Energy: 38.11356927230926 Eh 1037.12295 eV Virial components: Potential Energy : -152.29992056137917 Eh -4144.29153 eV Kinetic Energy : 76.00046447700970 Eh 2068.07778 eV Virial Ratio : 2.00393407605358 DFT components: N(Alpha) : 4.999999945349 electrons N(Beta) : 4.999999945349 electrons N(Total) : 9.999999890698 electrons E(X) : -7.171742421538 Eh E(C) : -0.405101561125 Eh E(XC) : -7.576843982663 Eh --------------- SCF CONVERGENCE --------------- Last Energy change ... -2.4920e-10 Tolerance : 1.0000e-08 Last MAX-Density change ... 6.0513e-07 Tolerance : 1.0000e-07 Last RMS-Density change ... 1.3686e-07 Tolerance : 5.0000e-09 Last DIIS Error ... 3.1404e-03 Tolerance : 5.0000e-07 Last Orbital Gradient ... 1.5854e-06 Tolerance : 1.0000e-05 Last Orbital Rotation ... 4.4950e-07 Tolerance : 1.0000e-05 Total SCF time: 0 days 0 hours 0 min 0 sec Finished LeanSCF after 0.6 sec Maximum memory used throughout the entire LEANSCF-calculation: 5.1 MB ------------------------- -------------------- FINAL SINGLE POINT ENERGY -76.299456084369 ------------------------- -------------------- ------------------------------------------------------------------------------ ORCA SCF GRADIENT CALCULATION ------------------------------------------------------------------------------ Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) done ( 0.2 sec) XC gradient ... done ( 0.1 sec) ------------------ CARTESIAN GRADIENT ------------------ 1 O : -0.000000180 -0.110628859 0.000000000 2 H : -0.055371787 0.055314386 -0.000000001 3 H : 0.055371968 0.055314473 0.000000001 Difference to translation invariance: : -0.0000000000 0.0000000001 0.0000000000 Difference to rotation invariance: : 0.0000000003 0.0000000023 0.0000000068 Norm of the Cartesian gradient ... 0.1564934711 RMS gradient ... 0.0521644904 MAX gradient ... 0.1106288595 ------- TIMINGS ------- Total SCF gradient time .... 0.345 sec Densities .... 0.000 sec ( 0.0%) One electron gradient .... 0.003 sec ( 0.9%) RI-J Coulomb gradient .... 0.053 sec ( 15.4%) COSX gradient .... 0.230 sec ( 66.6%) XC gradient .... 0.059 sec ( 17.1%) Maximum memory used throughout the entire SCFGRAD-calculation: 6.3 MB ------------------------------------------------------------------------------ ORCA GEOMETRY RELAXATION STEP ------------------------------------------------------------------------------ Reading the OPT-File .... done Getting information on internals .... done Copying old internal coords+grads .... done Making the new internal coordinates .... (2022 redundants) done Validating the new internal coordinates .... (2022 redundants) done Calculating the B-matrix .... done Calculating the G,G- and P matrices .... done Transforming gradient to internals .... done Projecting the internal gradient .... done Number of atoms .... 3 Number of internal coordinates .... 3 Current Energy .... -76.299456084 Eh Current gradient norm .... 0.156493471 Eh/bohr Maximum allowed component of the step .... 0.300 Current trust radius .... 0.675 Updating the Hessian (BFGS) .... done Forming the augmented Hessian .... done Diagonalizing the augmented Hessian .... done Last element of RFO vector .... 0.975868713 Lowest eigenvalues of augmented Hessian: -0.020668395 0.141603183 0.202606599 Length of the computed step .... 0.223757648 The final length of the internal step .... 0.223757648 Converting the step to Cartesian space: Initial RMS(Int)= 0.1291865382 Transforming coordinates: Iter 0: RMS(Cart)= 0.0495945527 RMS(Int)= 0.1279534144 Iter 5: RMS(Cart)= 0.0000001883 RMS(Int)= 0.0000004726 done Storing new coordinates .... done The predicted energy change is .... -0.010851605 Previously predicted energy change .... -0.026190354 Actually observed energy change .... -0.016486280 Ratio of predicted to observed change .... 0.629479089 New trust radius .... 0.675000000 .--------------------. ----------------------|Geometry convergence|------------------------- Item value Tolerance Converged --------------------------------------------------------------------- Energy change -0.0164862804 0.0000050000 NO RMS gradient 0.0655588423 0.0001000000 NO MAX gradient 0.0734315182 0.0003000000 NO RMS step 0.1291865382 0.0020000000 NO MAX step 0.1926439463 0.0040000000 NO ------------------------------------------------------------------------- ........................................................ Max(Bonds) 0.0426 Max(Angles) 11.04 Max(Dihed) 0.00 Max(Improp) 0.00 --------------------------------------------------------------------- The optimization has not yet converged - more geometry cycles are needed --------------------------------------------------------------------------- Redundant Internal Coordinates (Angstroem and degrees) Definition Value dE/dq Step New-Value ---------------------------------------------------------------------------- 1. B(H 1,O 0) 0.8974 -0.073431 0.0426 0.9400 2. B(H 2,O 0) 0.8974 -0.073432 0.0426 0.9400 3. A(H 1,O 0,H 2) 130.55 0.045930 -11.04 119.51 ---------------------------------------------------------------------------- Geometry step timings: Preparation and reading OPT file: 0.000 s ( 4.802 %) Internal coordinates : 0.000 s ( 3.107 %) B/P matrices and projection : 0.000 s (19.209 %) Hessian update/contruction : 0.000 s (34.181 %) Making the step : 0.000 s ( 9.322 %) Converting the step to Cartesian: 0.000 s ( 4.802 %) Storing new data : 0.000 s ( 5.085 %) Checking convergence : 0.000 s ( 6.215 %) Final printing : 0.000 s (13.277 %) Total time : 0.000 s Time for energy+gradient : 1.101 s Time for complete geometry iter : 1.116 s ************************************************************* * GEOMETRY OPTIMIZATION CYCLE 5 * ************************************************************* --------------------------------- CARTESIAN COORDINATES (ANGSTROEM) --------------------------------- O 0.000000 0.382292 0.000000 H 0.812039 -0.091146 0.000000 H -0.812039 -0.091146 0.000000 ---------------------------- CARTESIAN COORDINATES (A.U.) ---------------------------- NO LB ZA FRAG MASS X Y Z 0 O 8.0000 0 15.999 0.000000 0.722428 0.000000 1 H 1.0000 0 1.008 1.534531 -0.172241 0.000000 2 H 1.0000 0 1.008 -1.534531 -0.172241 0.000000 -------------------------------- INTERNAL COORDINATES (ANGSTROEM) -------------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 H 1 0 0 0.939973705993 0.00000000 0.00000000 H 1 2 0 0.939973921216 119.51354184 0.00000000 --------------------------- INTERNAL COORDINATES (A.U.) --------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 H 1 0 0 1.776292877414 0.00000000 0.00000000 H 1 2 0 1.776293284126 119.51354184 0.00000000 ------------------------------------------------------------------------------ ___ / \ - 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 ... 3 Number of basis functions ... 24 Number of shells ... 12 Maximum angular momentum ... 2 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 ... 71 # of shells in Aux-J ... 25 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 = 12 => 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 ... 78 Shell pairs after pre-screening ... 78 Total number of primitive shell pairs ... 272 Primitive shell pairs kept ... 265 la=0 lb=0: 28 shell pairs la=1 lb=0: 28 shell pairs la=1 lb=1: 10 shell pairs la=2 lb=0: 7 shell pairs la=2 lb=1: 4 shell pairs la=2 lb=2: 1 shell pairs Checking whether 4 symmetric matrices of dimension 24 fit in memory :Max Core in MB = 4096.00 MB in use = 3.23 MB left = 4092.77 MB needed = 0.01 Data fit in memory = YES Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 9.333355063118 Eh Diagonalization of the overlap matrix: Smallest eigenvalue ... 3.998e-02 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 ... 0.000 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 ... 12756 Total number of batches ... 201 Average number of points per batch ... 63 Average number of grid points per atom ... 4252 -------------------- 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 ... 1662 Total number of batches ... 14 Average number of points per batch ... 118 Average number of grid points per atom ... 554 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 ... 3508 Total number of batches ... 30 Average number of points per batch ... 116 Average number of grid points per atom ... 1169 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 ... 7754 Total number of batches ... 62 Average number of points per batch ... 125 Average number of grid points per atom ... 2585 UseSFitting ... on Grids setup in 0.1 sec Initializing property integral containers ... done ( 0.0 sec) SHARK setup successfully completed in 0.1 seconds Maximum memory used throughout the entire STARTUP-calculation: 8.8 MB Occupation numbers will be reassigned to an Aufbau configuration **** ENERGY FILE WAS UPDATED (water_opt_2.en.tmp) **** Finished Guess after 0.0 sec Maximum memory used throughout the entire GUESS-calculation: 5.5 MB ----------------------------------------D-I-I-S-------------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) ------------------------------------------------------------------------------------------- *** Starting incremental Fock matrix formation *** 1 -76.3109891667931919 0.00e+00 2.14e-03 1.32e-02 3.78e-02 0.700 0.1 2 -76.3120592176800727 -1.07e-03 1.91e-03 1.19e-02 2.56e-02 0.700 0.0 ***Turning on AO-DIIS*** 3 -76.3128525615271656 -7.93e-04 1.49e-03 8.54e-03 1.66e-02 0.700 0.0 4 -76.3134168323934574 -5.64e-04 3.75e-03 2.36e-02 1.32e-02 0.000 0.0 *** Initializing SOSCF *** ---------------------------------------S-O-S-C-F-------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) -------------------------------------------------------------------------------------- 5 -76.3148150715839648 -1.40e-03 2.07e-04 1.65e-03 9.97e-04 0.0 *** Restarting incremental Fock matrix formation *** 6 -76.3148145270004363 5.45e-07 1.28e-04 7.56e-04 3.19e-04 0.1 7 -76.3148149632292387 -4.36e-07 6.85e-05 5.22e-04 3.32e-04 0.0 8 -76.3148152551081722 -2.92e-07 2.30e-05 1.73e-04 4.86e-05 0.0 9 -76.3148152677242138 -1.26e-08 1.87e-06 1.09e-05 3.64e-06 0.0 10 -76.3148152682900189 -5.66e-10 6.44e-08 3.38e-07 5.70e-07 0.0 **** Energy Check signals convergence **** ***************************************************** * SUCCESS * * SCF CONVERGED AFTER 10 CYCLES * ***************************************************** Recomputing exchange energy using gridx3 ... done ( 0.057 sec) Old exchange energy : -1.795605993 Eh New exchange energy : -1.795589619 Eh Exchange energy change after final integration : 0.000016374 Eh Total energy after final integration : -76.314798895 Eh **** ENERGY FILE WAS UPDATED (water_opt_2.en.tmp) **** ---------------- TOTAL SCF ENERGY ---------------- Total Energy : -76.31479889472359 Eh -2076.63125 eV Components: Nuclear Repulsion : 9.33335506311822 Eh 253.97350 eV Electronic Energy : -85.64817033145479 Eh -2330.60520 eV One Electron Energy: -123.40957098075775 Eh -3358.14515 eV Two Electron Energy: 37.76140064930295 Eh 1027.53995 eV Virial components: Potential Energy : -152.18857903564654 Eh -4141.26177 eV Kinetic Energy : 75.87378014092295 Eh 2064.63052 eV Virial Ratio : 2.00581253172020 DFT components: N(Alpha) : 4.999999110172 electrons N(Beta) : 4.999999110172 electrons N(Total) : 9.999998220343 electrons E(X) : -7.140568895456 Eh E(C) : -0.403345607542 Eh E(XC) : -7.543914502998 Eh --------------- SCF CONVERGENCE --------------- Last Energy change ... 5.6581e-10 Tolerance : 1.0000e-08 Last MAX-Density change ... 3.3778e-07 Tolerance : 1.0000e-07 Last RMS-Density change ... 6.4435e-08 Tolerance : 5.0000e-09 Last DIIS Error ... 9.9653e-04 Tolerance : 5.0000e-07 Last Orbital Gradient ... 5.6987e-07 Tolerance : 1.0000e-05 Last Orbital Rotation ... 2.4229e-07 Tolerance : 1.0000e-05 Total SCF time: 0 days 0 hours 0 min 0 sec Finished LeanSCF after 0.6 sec Maximum memory used throughout the entire LEANSCF-calculation: 5.1 MB ------------------------- -------------------- FINAL SINGLE POINT ENERGY -76.314798894724 ------------------------- -------------------- ------------------------------------------------------------------------------ ORCA SCF GRADIENT CALCULATION ------------------------------------------------------------------------------ Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) done ( 0.2 sec) XC gradient ... done ( 0.1 sec) ------------------ CARTESIAN GRADIENT ------------------ 1 O : 0.000000277 -0.055326345 -0.000000010 2 H : -0.007939188 0.027663253 0.000000005 3 H : 0.007938911 0.027663092 0.000000005 Difference to translation invariance: : -0.0000000000 0.0000000001 -0.0000000000 Difference to rotation invariance: : -0.0000000089 0.0000000013 -0.0000000116 Norm of the Cartesian gradient ... 0.0686845225 RMS gradient ... 0.0228948408 MAX gradient ... 0.0553263446 ------- TIMINGS ------- Total SCF gradient time .... 0.340 sec Densities .... 0.000 sec ( 0.0%) One electron gradient .... 0.003 sec ( 0.9%) RI-J Coulomb gradient .... 0.053 sec ( 15.6%) COSX gradient .... 0.228 sec ( 67.1%) XC gradient .... 0.055 sec ( 16.3%) Maximum memory used throughout the entire SCFGRAD-calculation: 6.2 MB ------------------------------------------------------------------------------ ORCA GEOMETRY RELAXATION STEP ------------------------------------------------------------------------------ Reading the OPT-File .... done Getting information on internals .... done Copying old internal coords+grads .... done Making the new internal coordinates .... (2022 redundants) done Validating the new internal coordinates .... (2022 redundants) done Calculating the B-matrix .... done Calculating the G,G- and P matrices .... done Transforming gradient to internals .... done Projecting the internal gradient .... done Number of atoms .... 3 Number of internal coordinates .... 3 Current Energy .... -76.314798895 Eh Current gradient norm .... 0.068684522 Eh/bohr Maximum allowed component of the step .... 0.300 Current trust radius .... 0.675 Updating the Hessian (BFGS) .... done Forming the augmented Hessian .... done Diagonalizing the augmented Hessian .... done Last element of RFO vector .... 0.925758140 Lowest eigenvalues of augmented Hessian: -0.016062453 0.089928540 0.202606599 Length of the computed step .... 0.408439515 The final length of the internal step .... 0.306085643 Converting the step to Cartesian space: Initial RMS(Int)= 0.1767186281 Transforming coordinates: Iter 0: RMS(Cart)= 0.0824144004 RMS(Int)= 0.1754704303 Iter 5: RMS(Cart)= 0.0000044721 RMS(Int)= 0.0000068178 done Storing new coordinates .... done The predicted energy change is .... -0.008280861 Previously predicted energy change .... -0.010851605 Actually observed energy change .... -0.015342810 Ratio of predicted to observed change .... 1.413874783 New trust radius .... 0.675000000 .--------------------. ----------------------|Geometry convergence|------------------------- Item value Tolerance Converged --------------------------------------------------------------------- Energy change -0.0153428104 0.0000050000 NO RMS gradient 0.0265456161 0.0001000000 NO MAX gradient 0.0353471683 0.0003000000 NO RMS step 0.1767186281 0.0020000000 NO MAX step 0.3000000000 0.0040000000 NO ------------------------------------------------------------------------- ........................................................ Max(Bonds) 0.0227 Max(Angles) 17.19 Max(Dihed) 0.00 Max(Improp) 0.00 --------------------------------------------------------------------- The optimization has not yet converged - more geometry cycles are needed --------------------------------------------------------------------------- Redundant Internal Coordinates (Angstroem and degrees) Definition Value dE/dq Step New-Value ---------------------------------------------------------------------------- 1. B(H 1,O 0) 0.9400 -0.020792 0.0227 0.9627 2. B(H 2,O 0) 0.9400 -0.020792 0.0227 0.9627 3. A(H 1,O 0,H 2) 119.51 0.035347 -17.19 102.32 ---------------------------------------------------------------------------- Geometry step timings: Preparation and reading OPT file: 0.000 s ( 4.607 %) Internal coordinates : 0.000 s ( 2.439 %) B/P matrices and projection : 0.000 s (23.848 %) Hessian update/contruction : 0.000 s (31.165 %) Making the step : 0.000 s ( 7.588 %) Converting the step to Cartesian: 0.000 s ( 5.691 %) Storing new data : 0.000 s ( 4.336 %) Checking convergence : 0.000 s ( 5.962 %) Final printing : 0.000 s (14.363 %) Total time : 0.000 s Time for energy+gradient : 1.140 s Time for complete geometry iter : 1.155 s ************************************************************* * GEOMETRY OPTIMIZATION CYCLE 6 * ************************************************************* --------------------------------- CARTESIAN COORDINATES (ANGSTROEM) --------------------------------- O -0.000000 0.469149 0.000000 H 0.749872 -0.134574 0.000000 H -0.749872 -0.134574 0.000000 ---------------------------- CARTESIAN COORDINATES (A.U.) ---------------------------- NO LB ZA FRAG MASS X Y Z 0 O 8.0000 0 15.999 -0.000001 0.886562 0.000000 1 H 1.0000 0 1.008 1.417053 -0.254309 0.000000 2 H 1.0000 0 1.008 -1.417052 -0.254308 0.000000 -------------------------------- INTERNAL COORDINATES (ANGSTROEM) -------------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 H 1 0 0 0.962699500295 0.00000000 0.00000000 H 1 2 0 0.962698350072 102.32480813 0.00000000 --------------------------- INTERNAL COORDINATES (A.U.) --------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 H 1 0 0 1.819238404821 0.00000000 0.00000000 H 1 2 0 1.819236231213 102.32480813 0.00000000 ------------------------------------------------------------------------------ ___ / \ - 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 ... 3 Number of basis functions ... 24 Number of shells ... 12 Maximum angular momentum ... 2 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 ... 71 # of shells in Aux-J ... 25 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 = 12 => 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 ... 78 Shell pairs after pre-screening ... 78 Total number of primitive shell pairs ... 272 Primitive shell pairs kept ... 265 la=0 lb=0: 28 shell pairs la=1 lb=0: 28 shell pairs la=1 lb=1: 10 shell pairs la=2 lb=0: 7 shell pairs la=2 lb=1: 4 shell pairs la=2 lb=2: 1 shell pairs Checking whether 4 symmetric matrices of dimension 24 fit in memory :Max Core in MB = 4096.00 MB in use = 3.23 MB left = 4092.77 MB needed = 0.01 Data fit in memory = YES Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 9.147739446330 Eh Diagonalization of the overlap matrix: Smallest eigenvalue ... 3.748e-02 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 ... 0.000 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 ... 12752 Total number of batches ... 201 Average number of points per batch ... 63 Average number of grid points per atom ... 4251 -------------------- 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 ... 1648 Total number of batches ... 14 Average number of points per batch ... 117 Average number of grid points per atom ... 549 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 ... 3488 Total number of batches ... 29 Average number of points per batch ... 120 Average number of grid points per atom ... 1163 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 ... 7784 Total number of batches ... 62 Average number of points per batch ... 125 Average number of grid points per atom ... 2595 UseSFitting ... on Grids setup in 0.1 sec Initializing property integral containers ... done ( 0.0 sec) SHARK setup successfully completed in 0.1 seconds Maximum memory used throughout the entire STARTUP-calculation: 8.8 MB Occupation numbers will be reassigned to an Aufbau configuration **** ENERGY FILE WAS UPDATED (water_opt_2.en.tmp) **** Finished Guess after 0.0 sec Maximum memory used throughout the entire GUESS-calculation: 5.5 MB ----------------------------------------D-I-I-S-------------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) ------------------------------------------------------------------------------------------- *** Starting incremental Fock matrix formation *** 1 -76.3158417606932744 0.00e+00 2.67e-03 1.63e-02 4.25e-02 0.700 0.1 2 -76.3173609538680182 -1.52e-03 2.34e-03 1.43e-02 3.00e-02 0.700 0.0 ***Turning on AO-DIIS*** 3 -76.3184919299404498 -1.13e-03 1.80e-03 1.11e-02 2.11e-02 0.700 0.0 4 -76.3192976495033406 -8.06e-04 4.45e-03 2.67e-02 1.48e-02 0.000 0.0 *** Initializing SOSCF *** ---------------------------------------S-O-S-C-F-------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) -------------------------------------------------------------------------------------- 5 -76.3212639197654141 -1.97e-03 1.43e-04 1.15e-03 6.02e-04 0.0 *** Restarting incremental Fock matrix formation *** 6 -76.3212598979849020 4.02e-06 8.48e-05 5.71e-04 2.47e-04 0.1 7 -76.3212600608493119 -1.63e-07 4.83e-05 3.90e-04 2.59e-04 0.0 8 -76.3212602522721113 -1.91e-07 1.44e-05 1.15e-04 3.24e-05 0.0 9 -76.3212602566013345 -4.33e-09 1.41e-06 8.95e-06 2.83e-06 0.0 **** Energy Check signals convergence **** ***************************************************** * SUCCESS * * SCF CONVERGED AFTER 9 CYCLES * ***************************************************** Recomputing exchange energy using gridx3 ... done ( 0.057 sec) Old exchange energy : -1.790842336 Eh New exchange energy : -1.790796716 Eh Exchange energy change after final integration : 0.000045620 Eh Total energy after final integration : -76.321214636 Eh **** ENERGY FILE WAS UPDATED (water_opt_2.en.tmp) **** ---------------- TOTAL SCF ENERGY ---------------- Total Energy : -76.32121463648916 Eh -2076.80583 eV Components: Nuclear Repulsion : 9.14773944633045 Eh 248.92265 eV Electronic Energy : -85.46899970286947 Eh -2325.72972 eV One Electron Energy: -123.02890712479187 Eh -3347.78676 eV Two Electron Energy: 37.55990742192240 Eh 1022.05704 eV Virial components: Potential Energy : -152.16916265670278 Eh -4140.73343 eV Kinetic Energy : 75.84794802021361 Eh 2063.92759 eV Virial Ratio : 2.00623967593889 DFT components: N(Alpha) : 4.999998167511 electrons N(Beta) : 4.999998167511 electrons N(Total) : 9.999996335023 electrons E(X) : -7.125060038107 Eh E(C) : -0.402350177301 Eh E(XC) : -7.527410215408 Eh --------------- SCF CONVERGENCE --------------- Last Energy change ... 4.3292e-09 Tolerance : 1.0000e-08 Last MAX-Density change ... 8.9480e-06 Tolerance : 1.0000e-07 Last RMS-Density change ... 1.4089e-06 Tolerance : 5.0000e-09 Last DIIS Error ... 6.0238e-04 Tolerance : 5.0000e-07 Last Orbital Gradient ... 2.8276e-06 Tolerance : 1.0000e-05 Last Orbital Rotation ... 8.1637e-06 Tolerance : 1.0000e-05 Total SCF time: 0 days 0 hours 0 min 0 sec Finished LeanSCF after 0.6 sec Maximum memory used throughout the entire LEANSCF-calculation: 5.2 MB ------------------------- -------------------- FINAL SINGLE POINT ENERGY -76.321214636489 ------------------------- -------------------- ------------------------------------------------------------------------------ ORCA SCF GRADIENT CALCULATION ------------------------------------------------------------------------------ Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) done ( 0.2 sec) XC gradient ... done ( 0.1 sec) ------------------ CARTESIAN GRADIENT ------------------ 1 O : -0.000000919 -0.003557368 -0.000000006 2 H : -0.004551361 0.001778318 0.000000006 3 H : 0.004552279 0.001779050 -0.000000000 Difference to translation invariance: : -0.0000000000 0.0000000001 -0.0000000000 Difference to rotation invariance: : -0.0000000071 -0.0000000089 0.0000000117 Norm of the Cartesian gradient ... 0.0077730581 RMS gradient ... 0.0025910194 MAX gradient ... 0.0045522792 ------- TIMINGS ------- Total SCF gradient time .... 0.344 sec Densities .... 0.000 sec ( 0.0%) One electron gradient .... 0.003 sec ( 0.9%) RI-J Coulomb gradient .... 0.053 sec ( 15.4%) COSX gradient .... 0.233 sec ( 67.6%) XC gradient .... 0.055 sec ( 16.0%) Maximum memory used throughout the entire SCFGRAD-calculation: 6.2 MB ------------------------------------------------------------------------------ ORCA GEOMETRY RELAXATION STEP ------------------------------------------------------------------------------ Reading the OPT-File .... done Getting information on internals .... done Copying old internal coords+grads .... done Making the new internal coordinates .... (2022 redundants) done Validating the new internal coordinates .... (2022 redundants) done Calculating the B-matrix .... done Calculating the G,G- and P matrices .... done Transforming gradient to internals .... done Projecting the internal gradient .... done Number of atoms .... 3 Number of internal coordinates .... 3 Current Energy .... -76.321214636 Eh Current gradient norm .... 0.007773058 Eh/bohr Maximum allowed component of the step .... 0.300 Current trust radius .... 0.675 Updating the Hessian (BFGS) .... done Forming the augmented Hessian .... done Diagonalizing the augmented Hessian .... done Last element of RFO vector .... 0.999829941 Lowest eigenvalues of augmented Hessian: -0.000103018 0.131873852 0.202606599 Length of the computed step .... 0.018444664 The final length of the internal step .... 0.018444664 Converting the step to Cartesian space: Initial RMS(Int)= 0.0106490317 Transforming coordinates: Iter 0: RMS(Cart)= 0.0069699008 RMS(Int)= 0.0106441098 done Storing new coordinates .... done The predicted energy change is .... -0.000051527 Previously predicted energy change .... -0.008280861 Actually observed energy change .... -0.006415742 Ratio of predicted to observed change .... 0.774767507 New trust radius .... 0.700000000 .--------------------. ----------------------|Geometry convergence|------------------------- Item value Tolerance Converged --------------------------------------------------------------------- Energy change -0.0064157418 0.0000050000 NO RMS gradient 0.0041065751 0.0001000000 NO MAX gradient 0.0046615618 0.0003000000 NO RMS step 0.0106490317 0.0020000000 NO MAX step 0.0160259381 0.0040000000 NO ------------------------------------------------------------------------- ........................................................ Max(Bonds) 0.0034 Max(Angles) 0.92 Max(Dihed) 0.00 Max(Improp) 0.00 --------------------------------------------------------------------- The optimization has not yet converged - more geometry cycles are needed --------------------------------------------------------------------------- Redundant Internal Coordinates (Angstroem and degrees) Definition Value dE/dq Step New-Value ---------------------------------------------------------------------------- 1. B(H 1,O 0) 0.9627 -0.004660 0.0034 0.9661 2. B(H 2,O 0) 0.9627 -0.004662 0.0034 0.9661 3. A(H 1,O 0,H 2) 102.32 -0.002673 0.92 103.24 ---------------------------------------------------------------------------- Geometry step timings: Preparation and reading OPT file: 0.000 s ( 4.762 %) Internal coordinates : 0.000 s ( 2.976 %) B/P matrices and projection : 0.000 s (20.833 %) Hessian update/contruction : 0.000 s (31.548 %) Making the step : 0.000 s ( 8.929 %) Converting the step to Cartesian: 0.000 s ( 4.167 %) Storing new data : 0.000 s ( 5.357 %) Checking convergence : 0.000 s ( 7.440 %) Final printing : 0.000 s (13.988 %) Total time : 0.000 s Time for energy+gradient : 1.102 s Time for complete geometry iter : 1.116 s ************************************************************* * GEOMETRY OPTIMIZATION CYCLE 7 * ************************************************************* --------------------------------- CARTESIAN COORDINATES (ANGSTROEM) --------------------------------- O 0.000001 0.466544 0.000000 H 0.757363 -0.133272 0.000000 H -0.757364 -0.133272 0.000000 ---------------------------- CARTESIAN COORDINATES (A.U.) ---------------------------- NO LB ZA FRAG MASS X Y Z 0 O 8.0000 0 15.999 0.000001 0.881641 0.000000 1 H 1.0000 0 1.008 1.431210 -0.251847 0.000000 2 H 1.0000 0 1.008 -1.431211 -0.251848 0.000000 -------------------------------- INTERNAL COORDINATES (ANGSTROEM) -------------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 H 1 0 0 0.966114737331 0.00000000 0.00000000 H 1 2 0 0.966116465887 103.24302675 0.00000000 --------------------------- INTERNAL COORDINATES (A.U.) --------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 H 1 0 0 1.825692267500 0.00000000 0.00000000 H 1 2 0 1.825695533999 103.24302675 0.00000000 ------------------------------------------------------------------------------ ___ / \ - 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 ... 3 Number of basis functions ... 24 Number of shells ... 12 Maximum angular momentum ... 2 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 ... 71 # of shells in Aux-J ... 25 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 = 12 => 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 ... 78 Shell pairs after pre-screening ... 78 Total number of primitive shell pairs ... 272 Primitive shell pairs kept ... 265 la=0 lb=0: 28 shell pairs la=1 lb=0: 28 shell pairs la=1 lb=1: 10 shell pairs la=2 lb=0: 7 shell pairs la=2 lb=1: 4 shell pairs la=2 lb=2: 1 shell pairs Checking whether 4 symmetric matrices of dimension 24 fit in memory :Max Core in MB = 4096.00 MB in use = 3.23 MB left = 4092.77 MB needed = 0.01 Data fit in memory = YES Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 9.113145847989 Eh Diagonalization of the overlap matrix: Smallest eigenvalue ... 3.793e-02 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 ... 0.000 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 ... 12754 Total number of batches ... 201 Average number of points per batch ... 63 Average number of grid points per atom ... 4251 -------------------- 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 ... 1650 Total number of batches ... 14 Average number of points per batch ... 117 Average number of grid points per atom ... 550 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 ... 3494 Total number of batches ... 29 Average number of points per batch ... 120 Average number of grid points per atom ... 1165 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 ... 7784 Total number of batches ... 62 Average number of points per batch ... 125 Average number of grid points per atom ... 2595 UseSFitting ... on Grids setup in 0.0 sec Initializing property integral containers ... done ( 0.0 sec) SHARK setup successfully completed in 0.1 seconds Maximum memory used throughout the entire STARTUP-calculation: 8.8 MB Occupation numbers will be reassigned to an Aufbau configuration **** ENERGY FILE WAS UPDATED (water_opt_2.en.tmp) **** Finished Guess after 0.0 sec Maximum memory used throughout the entire GUESS-calculation: 5.5 MB ----------------------------------------D-I-I-S-------------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) ------------------------------------------------------------------------------------------- *** Starting incremental Fock matrix formation *** *** Initializing SOSCF *** ---------------------------------------S-O-S-C-F-------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) -------------------------------------------------------------------------------------- 1 -76.3212941946241017 0.00e+00 5.57e-04 3.54e-03 2.20e-04 0.0 *** Restarting incremental Fock matrix formation *** 2 -76.3213129109966815 -1.87e-05 1.29e-04 7.12e-04 3.61e-04 0.0 3 -76.3213133073513745 -3.96e-07 5.62e-05 3.96e-04 3.62e-04 0.0 4 -76.3213136598974984 -3.53e-07 1.94e-05 1.64e-04 7.91e-05 0.0 5 -76.3213136821647424 -2.23e-08 2.73e-06 2.47e-05 1.31e-05 0.0 6 -76.3213136832300023 -1.07e-09 3.66e-07 1.91e-06 2.18e-06 0.0 **** Energy Check signals convergence **** ***************************************************** * SUCCESS * * SCF CONVERGED AFTER 6 CYCLES * ***************************************************** Recomputing exchange energy using gridx3 ... done ( 0.054 sec) Old exchange energy : -1.790144946 Eh New exchange energy : -1.790099912 Eh Exchange energy change after final integration : 0.000045034 Eh Total energy after final integration : -76.321268649 Eh **** ENERGY FILE WAS UPDATED (water_opt_2.en.tmp) **** ---------------- TOTAL SCF ENERGY ---------------- Total Energy : -76.32126864932329 Eh -2076.80730 eV Components: Nuclear Repulsion : 9.11314584798855 Eh 247.98131 eV Electronic Energy : -85.43445953138553 Eh -2324.78983 eV One Electron Energy: -122.97064243656769 Eh -3346.20130 eV Two Electron Energy: 37.53618290518216 Eh 1021.41146 eV Virial components: Potential Energy : -152.15616444063772 Eh -4140.37973 eV Kinetic Energy : 75.83489579131444 Eh 2063.57242 eV Virial Ratio : 2.00641357587340 DFT components: N(Alpha) : 4.999998164155 electrons N(Beta) : 4.999998164155 electrons N(Total) : 9.999996328311 electrons E(X) : -7.122643418733 Eh E(C) : -0.402226895075 Eh E(XC) : -7.524870313808 Eh --------------- SCF CONVERGENCE --------------- Last Energy change ... 1.0653e-09 Tolerance : 1.0000e-08 Last MAX-Density change ... 1.9140e-06 Tolerance : 1.0000e-07 Last RMS-Density change ... 3.6612e-07 Tolerance : 5.0000e-09 Last DIIS Error ... 2.0976e-03 Tolerance : 5.0000e-07 Last Orbital Gradient ... 2.1775e-06 Tolerance : 1.0000e-05 Last Orbital Rotation ... 1.0292e-06 Tolerance : 1.0000e-05 Total SCF time: 0 days 0 hours 0 min 0 sec Finished LeanSCF after 0.4 sec Maximum memory used throughout the entire LEANSCF-calculation: 5.2 MB ------------------------- -------------------- FINAL SINGLE POINT ENERGY -76.321268649323 ------------------------- -------------------- ------------------------------------------------------------------------------ ORCA SCF GRADIENT CALCULATION ------------------------------------------------------------------------------ Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) done ( 0.2 sec) XC gradient ... done ( 0.1 sec) ------------------ CARTESIAN GRADIENT ------------------ 1 O : 0.000001366 -0.001190971 0.000000007 2 H : -0.000430709 0.000596039 -0.000000006 3 H : 0.000429342 0.000594933 -0.000000001 Difference to translation invariance: : 0.0000000000 0.0000000001 0.0000000000 Difference to rotation invariance: : 0.0000000081 0.0000000060 0.0000000325 Norm of the Cartesian gradient ... 0.0015803374 RMS gradient ... 0.0005267791 MAX gradient ... 0.0011909713 ------- TIMINGS ------- Total SCF gradient time .... 0.326 sec Densities .... 0.000 sec ( 0.0%) One electron gradient .... 0.003 sec ( 0.9%) RI-J Coulomb gradient .... 0.051 sec ( 15.5%) COSX gradient .... 0.220 sec ( 67.4%) XC gradient .... 0.053 sec ( 16.1%) Maximum memory used throughout the entire SCFGRAD-calculation: 6.2 MB ------------------------------------------------------------------------------ ORCA GEOMETRY RELAXATION STEP ------------------------------------------------------------------------------ Reading the OPT-File .... done Getting information on internals .... done Copying old internal coords+grads .... done Making the new internal coordinates .... (2022 redundants) done Validating the new internal coordinates .... (2022 redundants) done Calculating the B-matrix .... done Calculating the G,G- and P matrices .... done Transforming gradient to internals .... done Projecting the internal gradient .... done Number of atoms .... 3 Number of internal coordinates .... 3 Current Energy .... -76.321268649 Eh Current gradient norm .... 0.001580337 Eh/bohr Maximum allowed component of the step .... 0.300 Current trust radius .... 0.700 Updating the Hessian (BFGS) .... done Forming the augmented Hessian .... done Diagonalizing the augmented Hessian .... done Last element of RFO vector .... 0.999993148 Lowest eigenvalues of augmented Hessian: -0.000003287 0.153369472 0.202606645 Length of the computed step .... 0.003701973 The final length of the internal step .... 0.003701973 Converting the step to Cartesian space: Initial RMS(Int)= 0.0021373350 Transforming coordinates: Iter 0: RMS(Cart)= 0.0008707443 RMS(Int)= 0.0021371389 done Storing new coordinates .... done The predicted energy change is .... -0.000001644 Previously predicted energy change .... -0.000051527 Actually observed energy change .... -0.000054013 Ratio of predicted to observed change .... 1.048252354 New trust radius .... 0.700000000 .--------------------. ----------------------|Geometry convergence|------------------------- Item value Tolerance Converged --------------------------------------------------------------------- Energy change -0.0000540128 0.0000050000 NO RMS gradient 0.0006143533 0.0001000000 NO MAX gradient 0.0007076928 0.0003000000 NO RMS step 0.0021373350 0.0020000000 NO MAX step 0.0029753216 0.0040000000 YES ------------------------------------------------------------------------- ........................................................ Max(Bonds) 0.0008 Max(Angles) 0.17 Max(Dihed) 0.00 Max(Improp) 0.00 --------------------------------------------------------------------- The optimization has not yet converged - more geometry cycles are needed --------------------------------------------------------------------------- Redundant Internal Coordinates (Angstroem and degrees) Definition Value dE/dq Step New-Value ---------------------------------------------------------------------------- 1. B(H 1,O 0) 0.9661 -0.000708 0.0008 0.9669 2. B(H 2,O 0) 0.9661 -0.000706 0.0008 0.9669 3. A(H 1,O 0,H 2) 103.24 0.000365 -0.17 103.07 ---------------------------------------------------------------------------- Geometry step timings: Preparation and reading OPT file: 0.000 s ( 3.881 %) Internal coordinates : 0.000 s ( 2.985 %) B/P matrices and projection : 0.000 s (19.104 %) Hessian update/contruction : 0.000 s (34.925 %) Making the step : 0.000 s ( 8.657 %) Converting the step to Cartesian: 0.000 s ( 4.179 %) Storing new data : 0.000 s ( 5.075 %) Checking convergence : 0.000 s ( 8.060 %) Final printing : 0.000 s (13.134 %) Total time : 0.000 s Time for energy+gradient : 0.965 s Time for complete geometry iter : 0.982 s ************************************************************* * GEOMETRY OPTIMIZATION CYCLE 8 * ************************************************************* --------------------------------- CARTESIAN COORDINATES (ANGSTROEM) --------------------------------- O -0.000001 0.467637 0.000000 H 0.757116 -0.133819 0.000000 H -0.757115 -0.133818 0.000000 ---------------------------- CARTESIAN COORDINATES (A.U.) ---------------------------- NO LB ZA FRAG MASS X Y Z 0 O 8.0000 0 15.999 -0.000002 0.883705 0.000000 1 H 1.0000 0 1.008 1.430743 -0.252881 0.000000 2 H 1.0000 0 1.008 -1.430741 -0.252879 0.000000 -------------------------------- INTERNAL COORDINATES (ANGSTROEM) -------------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 H 1 0 0 0.966941269914 0.00000000 0.00000000 H 1 2 0 0.966938390568 103.07255337 0.00000000 --------------------------- INTERNAL COORDINATES (A.U.) --------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 H 1 0 0 1.827254187723 0.00000000 0.00000000 H 1 2 0 1.827248746548 103.07255337 0.00000000 ------------------------------------------------------------------------------ ___ / \ - 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 ... 3 Number of basis functions ... 24 Number of shells ... 12 Maximum angular momentum ... 2 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 ... 71 # of shells in Aux-J ... 25 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 = 12 => 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 ... 78 Shell pairs after pre-screening ... 78 Total number of primitive shell pairs ... 272 Primitive shell pairs kept ... 265 la=0 lb=0: 28 shell pairs la=1 lb=0: 28 shell pairs la=1 lb=1: 10 shell pairs la=2 lb=0: 7 shell pairs la=2 lb=1: 4 shell pairs la=2 lb=2: 1 shell pairs Checking whether 4 symmetric matrices of dimension 24 fit in memory :Max Core in MB = 4096.00 MB in use = 3.23 MB left = 4092.77 MB needed = 0.01 Data fit in memory = YES Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 9.105789846202 Eh Diagonalization of the overlap matrix: Smallest eigenvalue ... 3.795e-02 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 ... 0.000 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 ... 12754 Total number of batches ... 201 Average number of points per batch ... 63 Average number of grid points per atom ... 4251 -------------------- 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 ... 1648 Total number of batches ... 14 Average number of points per batch ... 117 Average number of grid points per atom ... 549 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 ... 3492 Total number of batches ... 29 Average number of points per batch ... 120 Average number of grid points per atom ... 1164 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 ... 7784 Total number of batches ... 62 Average number of points per batch ... 125 Average number of grid points per atom ... 2595 UseSFitting ... on Grids setup in 0.1 sec Initializing property integral containers ... done ( 0.0 sec) SHARK setup successfully completed in 0.1 seconds Maximum memory used throughout the entire STARTUP-calculation: 8.8 MB Occupation numbers will be reassigned to an Aufbau configuration **** ENERGY FILE WAS UPDATED (water_opt_2.en.tmp) **** Finished Guess after 0.0 sec Maximum memory used throughout the entire GUESS-calculation: 5.5 MB ----------------------------------------D-I-I-S-------------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) ------------------------------------------------------------------------------------------- *** Starting incremental Fock matrix formation *** *** Initializing SOSCF *** ---------------------------------------S-O-S-C-F-------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) -------------------------------------------------------------------------------------- 1 -76.3213149607585137 0.00e+00 1.11e-04 7.51e-04 6.46e-05 0.1 *** Restarting incremental Fock matrix formation *** 2 -76.3213158056018983 -8.45e-07 3.98e-05 2.86e-04 1.25e-04 0.1 3 -76.3213158552374580 -4.96e-08 2.16e-05 1.63e-04 1.19e-04 0.0 4 -76.3213158936756315 -3.84e-08 7.43e-06 5.20e-05 1.61e-05 0.0 5 -76.3213158952766690 -1.60e-09 8.44e-07 4.74e-06 3.14e-06 0.0 **** Energy Check signals convergence **** ***************************************************** * SUCCESS * * SCF CONVERGED AFTER 5 CYCLES * ***************************************************** Recomputing exchange energy using gridx3 ... done ( 0.056 sec) Old exchange energy : -1.789970367 Eh New exchange energy : -1.789924142 Eh Exchange energy change after final integration : 0.000046225 Eh Total energy after final integration : -76.321269671 Eh **** ENERGY FILE WAS UPDATED (water_opt_2.en.tmp) **** ---------------- TOTAL SCF ENERGY ---------------- Total Energy : -76.32126967056746 Eh -2076.80733 eV Components: Nuclear Repulsion : 9.10578984620227 Eh 247.78114 eV Electronic Energy : -85.42710574142475 Eh -2324.58973 eV One Electron Energy: -122.95700204095344 Eh -3345.83012 eV Two Electron Energy: 37.52989629952869 Eh 1021.24040 eV Virial components: Potential Energy : -152.15409131720793 Eh -4140.32331 eV Kinetic Energy : 75.83282164664045 Eh 2063.51598 eV Virial Ratio : 2.00644111630453 DFT components: N(Alpha) : 4.999998161568 electrons N(Beta) : 4.999998161568 electrons N(Total) : 9.999996323136 electrons E(X) : -7.122068139600 Eh E(C) : -0.402195630188 Eh E(XC) : -7.524263769788 Eh --------------- SCF CONVERGENCE --------------- Last Energy change ... 1.6010e-09 Tolerance : 1.0000e-08 Last MAX-Density change ... 4.7394e-06 Tolerance : 1.0000e-07 Last RMS-Density change ... 8.4408e-07 Tolerance : 5.0000e-09 Last DIIS Error ... 5.9423e-04 Tolerance : 5.0000e-07 Last Orbital Gradient ... 3.1443e-06 Tolerance : 1.0000e-05 Last Orbital Rotation ... 3.2560e-06 Tolerance : 1.0000e-05 Total SCF time: 0 days 0 hours 0 min 0 sec Finished LeanSCF after 0.4 sec Maximum memory used throughout the entire LEANSCF-calculation: 5.3 MB ------------------------- -------------------- FINAL SINGLE POINT ENERGY -76.321269670567 ------------------------- -------------------- ------------------------------------------------------------------------------ ORCA SCF GRADIENT CALCULATION ------------------------------------------------------------------------------ Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) done ( 0.2 sec) XC gradient ... done ( 0.1 sec) ------------------ CARTESIAN GRADIENT ------------------ 1 O : -0.000002295 0.000037883 -0.000000002 2 H : 0.000008252 -0.000019849 -0.000000000 3 H : -0.000005957 -0.000018034 0.000000002 Difference to translation invariance: : 0.0000000000 0.0000000001 0.0000000000 Difference to rotation invariance: : -0.0000000022 0.0000000034 0.0000000116 Norm of the Cartesian gradient ... 0.0000475730 RMS gradient ... 0.0000158577 MAX gradient ... 0.0000378832 ------- TIMINGS ------- Total SCF gradient time .... 0.340 sec Densities .... 0.000 sec ( 0.0%) One electron gradient .... 0.003 sec ( 0.9%) RI-J Coulomb gradient .... 0.053 sec ( 15.6%) COSX gradient .... 0.229 sec ( 67.4%) XC gradient .... 0.054 sec ( 16.0%) Maximum memory used throughout the entire SCFGRAD-calculation: 6.2 MB ------------------------------------------------------------------------------ ORCA GEOMETRY RELAXATION STEP ------------------------------------------------------------------------------ Reading the OPT-File .... done Getting information on internals .... done Copying old internal coords+grads .... done Making the new internal coordinates .... (2022 redundants) done Validating the new internal coordinates .... (2022 redundants) done Calculating the B-matrix .... done Calculating the G,G- and P matrices .... done Transforming gradient to internals .... done Projecting the internal gradient .... done Number of atoms .... 3 Number of internal coordinates .... 3 Current Energy .... -76.321269671 Eh Current gradient norm .... 0.000047573 Eh/bohr Maximum allowed component of the step .... 0.300 Current trust radius .... 0.700 Updating the Hessian (BFGS) .... done Forming the augmented Hessian .... done Diagonalizing the augmented Hessian .... done Last element of RFO vector .... 0.999999989 Lowest eigenvalues of augmented Hessian: -0.000000004 0.157503632 0.202611255 Length of the computed step .... 0.000145487 The final length of the internal step .... 0.000145487 Converting the step to Cartesian space: Initial RMS(Int)= 0.0000839968 Transforming coordinates: Iter 0: RMS(Cart)= 0.0000387599 RMS(Int)= 0.0000839971 done Storing new coordinates .... done The predicted energy change is .... -0.000000002 Previously predicted energy change .... -0.000001644 Actually observed energy change .... -0.000001021 Ratio of predicted to observed change .... 0.621310284 New trust radius .... 0.700000000 .--------------------. ----------------------|Geometry convergence|------------------------- Item value Tolerance Converged --------------------------------------------------------------------- Energy change -0.0000010212 0.0000050000 YES RMS gradient 0.0000179624 0.0001000000 YES MAX gradient 0.0000190259 0.0003000000 YES RMS step 0.0000839968 0.0020000000 YES MAX step 0.0001329863 0.0040000000 YES ------------------------------------------------------------------------- ........................................................ Max(Bonds) 0.0000 Max(Angles) 0.01 Max(Dihed) 0.00 Max(Improp) 0.00 --------------------------------------------------------------------- ***********************HURRAY******************** *** THE OPTIMIZATION HAS CONVERGED *** ************************************************* --------------------------------------------------------------------------- Redundant Internal Coordinates --- Optimized Parameters --- (Angstroem and degrees) Definition OldVal dE/dq Step FinalVal ---------------------------------------------------------------------------- 1. B(H 1,O 0) 0.9669 0.000019 -0.0000 0.9669 2. B(H 2,O 0) 0.9669 0.000016 -0.0000 0.9669 3. A(H 1,O 0,H 2) 103.07 -0.000019 0.01 103.08 ---------------------------------------------------------------------------- Geometry step timings: Preparation and reading OPT file: 0.000 s ( 4.819 %) Internal coordinates : 0.000 s ( 3.012 %) B/P matrices and projection : 0.000 s (21.084 %) Hessian update/contruction : 0.000 s (31.325 %) Making the step : 0.000 s ( 9.036 %) Converting the step to Cartesian: 0.000 s ( 4.217 %) Storing new data : 0.000 s ( 5.120 %) Checking convergence : 0.000 s ( 6.928 %) Final printing : 0.000 s (14.458 %) Total time : 0.000 s ******************************************************* *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** *** (AFTER 8 CYCLES) *** ******************************************************* --------------------------------- CARTESIAN COORDINATES (ANGSTROEM) --------------------------------- O 0.000002 0.467594 0.000000 H 0.757138 -0.133796 0.000000 H -0.757140 -0.133798 0.000000 ---------------------------- CARTESIAN COORDINATES (A.U.) ---------------------------- NO LB ZA FRAG MASS X Y Z 0 O 8.0000 0 15.999 0.000003 0.883625 0.000000 1 H 1.0000 0 1.008 1.430784 -0.252838 0.000000 2 H 1.0000 0 1.008 -1.430787 -0.252841 0.000000 -------------------------------- INTERNAL COORDINATES (ANGSTROEM) -------------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 H 1 0 0 0.966915809014 0.00000000 0.00000000 H 1 2 0 0.966920320436 103.08017293 0.00000000 --------------------------- INTERNAL COORDINATES (A.U.) --------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 H 1 0 0 1.827206073596 0.00000000 0.00000000 H 1 2 0 1.827214598947 103.08017293 0.00000000 --------------------- BASIS SET INFORMATION --------------------- There are 2 groups of distinct atoms Group 1 Type O : 7s4p1d contracted to 3s2p1d pattern {511/31/1} Group 2 Type H : 4s1p contracted to 2s1p pattern {31/1} Atom 0O basis set group => 1 Atom 1H basis set group => 2 Atom 2H basis set group => 2 --------------------------------- AUXILIARY/J BASIS SET INFORMATION --------------------------------- There are 2 groups of distinct atoms Group 1 Type O : 12s5p4d2f1g contracted to 6s4p3d1f1g pattern {711111/2111/211/2/1} Group 2 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} Atom 0O basis set group => 1 Atom 1H basis set group => 2 Atom 2H basis set group => 2 ------------------------------------------------------------------------------ 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 ... 3 Number of basis functions ... 24 Number of shells ... 12 Maximum angular momentum ... 2 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 ... 71 # of shells in Aux-J ... 25 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 = 12 => 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 ... 78 Shell pairs after pre-screening ... 78 Total number of primitive shell pairs ... 272 Primitive shell pairs kept ... 265 la=0 lb=0: 28 shell pairs la=1 lb=0: 28 shell pairs la=1 lb=1: 10 shell pairs la=2 lb=0: 7 shell pairs la=2 lb=1: 4 shell pairs la=2 lb=2: 1 shell pairs Checking whether 4 symmetric matrices of dimension 24 fit in memory :Max Core in MB = 4096.00 MB in use = 3.23 MB left = 4092.77 MB needed = 0.01 Data fit in memory = YES Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 9.105976360910 Eh Diagonalization of the overlap matrix: Smallest eigenvalue ... 3.795e-02 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 ... 0.000 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 ... 12754 Total number of batches ... 201 Average number of points per batch ... 63 Average number of grid points per atom ... 4251 -------------------- 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 ... 1648 Total number of batches ... 14 Average number of points per batch ... 117 Average number of grid points per atom ... 549 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 ... 3492 Total number of batches ... 29 Average number of points per batch ... 120 Average number of grid points per atom ... 1164 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 ... 7784 Total number of batches ... 62 Average number of points per batch ... 125 Average number of grid points per atom ... 2595 UseSFitting ... on Grids setup in 0.1 sec Initializing property integral containers ... done ( 0.0 sec) SHARK setup successfully completed in 0.1 seconds Maximum memory used throughout the entire STARTUP-calculation: 8.8 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 .... 71 RIJ-COSX (HFX calculated with COS-X)).... on General Settings: Integral files IntName .... water_opt_2 Hartree-Fock type HFTyp .... RHF Total Charge Charge .... 0 Multiplicity Mult .... 1 Number of Electrons NEL .... 10 Basis Dimension Dim .... 24 Nuclear Repulsion ENuc .... 9.1059763609 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 .... 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: MOREAD --------------------- Guess MOs are being read from file: water_opt_2.gbw 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 ( 0.0 sec) ------------------ **** ENERGY FILE WAS UPDATED (water_opt_2.en.tmp) **** Finished Guess after 0.0 sec Maximum memory used throughout the entire GUESS-calculation: 5.5 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 *** *** Initializing SOSCF *** ---------------------------------------S-O-S-C-F-------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) -------------------------------------------------------------------------------------- 1 -76.3213158757294110 0.00e+00 4.24e-06 2.83e-05 2.13e-06 0.1 *** Restarting incremental Fock matrix formation *** 2 -76.3213158769767119 -1.25e-09 1.33e-06 8.28e-06 4.11e-06 0.1 3 -76.3213158769227817 5.39e-11 7.21e-07 5.54e-06 3.08e-06 0.0 **** Energy Check signals convergence **** ***************************************************** * SUCCESS * * SCF CONVERGED AFTER 3 CYCLES * ***************************************************** Recomputing exchange energy using gridx3 ... done ( 0.057 sec) Old exchange energy : -1.789974805 Eh New exchange energy : -1.789928216 Eh Exchange energy change after final integration : 0.000046590 Eh Total energy after final integration : -76.321269288 Eh **** ENERGY FILE WAS UPDATED (water_opt_2.en.tmp) **** ---------------- TOTAL SCF ENERGY ---------------- Total Energy : -76.32126928751173 Eh -2076.80732 eV Components: Nuclear Repulsion : 9.10597636090973 Eh 247.78621 eV Electronic Energy : -85.42729223799675 Eh -2324.59480 eV One Electron Energy: -122.95736683028701 Eh -3345.84005 eV Two Electron Energy: 37.53007459229026 Eh 1021.24525 eV Virial components: Potential Energy : -152.15414112900271 Eh -4140.32467 eV Kinetic Energy : 75.83287184149100 Eh 2063.51735 eV Virial Ratio : 2.00644044507561 DFT components: N(Alpha) : 4.999998161672 electrons N(Beta) : 4.999998161672 electrons N(Total) : 9.999996323343 electrons E(X) : -7.122083941563 Eh E(C) : -0.402196501793 Eh E(XC) : -7.524280443355 Eh --------------- SCF CONVERGENCE --------------- Last Energy change ... -5.3930e-11 Tolerance : 1.0000e-08 Last MAX-Density change ... 5.5413e-06 Tolerance : 1.0000e-07 Last RMS-Density change ... 7.2090e-07 Tolerance : 5.0000e-09 Last DIIS Error ... 1.9390e-05 Tolerance : 5.0000e-07 Last Orbital Gradient ... 3.0763e-06 Tolerance : 1.0000e-05 Last Orbital Rotation ... 2.9426e-06 Tolerance : 1.0000e-05 ---------------- ORBITAL ENERGIES ---------------- NO OCC E(Eh) E(eV) 0 2.0000 -19.116105 -520.1757 1 2.0000 -0.976139 -26.5621 2 2.0000 -0.508032 -13.8243 3 2.0000 -0.364389 -9.9155 4 2.0000 -0.288147 -7.8409 5 0.0000 0.047713 1.2983 6 0.0000 0.126621 3.4455 7 0.0000 0.558298 15.1921 8 0.0000 0.623850 16.9758 9 0.0000 0.920749 25.0549 10 0.0000 0.923571 25.1316 11 0.0000 1.010163 27.4879 12 0.0000 1.098311 29.8866 13 0.0000 1.351330 36.7716 14 0.0000 1.398808 38.0635 15 0.0000 1.545613 42.0583 *Only the first 10 virtual orbitals were printed. ******************************** * MULLIKEN POPULATION ANALYSIS * ******************************** ----------------------- MULLIKEN ATOMIC CHARGES ----------------------- 0 O : -0.293611 1 H : 0.146805 2 H : 0.146806 Sum of atomic charges: 0.0000000 -------------------------------- MULLIKEN REDUCED ORBITAL CHARGES -------------------------------- 0 O s : 3.686884 s : 3.686884 pz : 1.959331 p : 4.595809 px : 1.144425 py : 1.492053 dz2 : 0.001929 d : 0.010918 dxz : 0.000000 dyz : 0.001219 dx2y2 : 0.000369 dxy : 0.007402 1 H s : 0.782768 s : 0.782768 pz : 0.019725 p : 0.070428 px : 0.028614 py : 0.022088 2 H s : 0.782767 s : 0.782767 pz : 0.019725 p : 0.070427 px : 0.028614 py : 0.022088 ******************************* * LOEWDIN POPULATION ANALYSIS * ******************************* ---------------------- LOEWDIN ATOMIC CHARGES ---------------------- 0 O : -0.150136 1 H : 0.075067 2 H : 0.075069 ------------------------------- LOEWDIN REDUCED ORBITAL CHARGES ------------------------------- 0 O s : 3.439979 s : 3.439979 pz : 1.892305 p : 4.690014 px : 1.230180 py : 1.567530 dz2 : 0.004226 d : 0.020143 dxz : 0.000000 dyz : 0.000370 dx2y2 : 0.000021 dxy : 0.015526 1 H s : 0.750038 s : 0.750038 pz : 0.053663 p : 0.174895 px : 0.059761 py : 0.061471 2 H s : 0.750038 s : 0.750038 pz : 0.053662 p : 0.174893 px : 0.059761 py : 0.061470 ***************************** * 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 O 8.2936 8.0000 -0.2936 2.0163 2.0163 0.0000 1 H 0.8532 1.0000 0.1468 1.0136 1.0136 0.0000 2 H 0.8532 1.0000 0.1468 1.0136 1.0136 -0.0000 Mayer bond orders larger than 0.100000 B( 0-O , 1-H ) : 1.0081 B( 0-O , 2-H ) : 1.0081 ------- TIMINGS ------- Total SCF time: 0 days 0 hours 0 min 0 sec Total time .... 0.307 sec Sum of individual times .... 0.253 sec ( 82.4%) SCF preparation .... 0.040 sec ( 13.2%) Fock matrix formation .... 0.204 sec ( 66.4%) Startup .... 0.000 sec ( 0.1% of F) Split-RI-J .... 0.006 sec ( 2.8% of F) Chain of spheres X .... 0.182 sec ( 89.4% of F) XC integration .... 0.061 sec ( 30.0% of F) Basis function eval. .... 0.025 sec ( 41.7% of XC) Density eval. .... 0.007 sec ( 11.2% of XC) XC-Functional eval. .... 0.017 sec ( 28.4% of XC) XC-Potential eval. .... 0.007 sec ( 10.7% of XC) Diagonalization .... 0.000 sec ( 0.0%) Density matrix formation .... 0.000 sec ( 0.1%) Total Energy calculation .... 0.000 sec ( 0.0%) Population analysis .... 0.007 sec ( 2.3%) Orbital Transformation .... 0.000 sec ( 0.1%) Orbital Orthonormalization .... 0.000 sec ( 0.0%) DIIS solution .... 0.000 sec ( 0.1%) SOSCF solution .... 0.001 sec ( 0.2%) Finished LeanSCF after 0.3 sec Maximum memory used throughout the entire LEANSCF-calculation: 5.3 MB ------------------------- -------------------- FINAL SINGLE POINT ENERGY -76.321269287512 ------------------------- -------------------- *** OPTIMIZATION RUN DONE *** ------------------------------------------------------------------------------ ORCA PROPERTY CALCULATIONS ------------------------------------------------------------------------------ GBWName ... water_opt_2.gbw Number of atoms ... 3 Number of basis functions ... 24 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 ... 0.000002 0.756447 0.000000 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 : -76.3212692875117256 Eh Basis : AO X Y Z Electronic contribution: 0.000002753 0.212699424 -0.000000000 Nuclear contribution : -0.000003916 -1.001148508 0.000000000 ----------------------------------------- Total Dipole Moment : -0.000001163 -0.788449084 -0.000000000 ----------------------------------------- Magnitude (a.u.) : 0.788449084 Magnitude (Debye) : 2.004078304 -------------------- Rotational spectrum -------------------- Rotational constants in cm-1: 26.033555 14.586627 9.348598 Rotational constants in MHz : 780466.338742 437296.065832 280263.915329 Dipole components along the rotational axes: x,y,z [a.u.] : 0.000007 -0.788449 -0.000000 x,y,z [Debye]: 0.000017 -2.004078 -0.000000 Dipole moment calculation done in 0.0 sec Maximum memory used throughout the entire PROP-calculation: 3.6 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 water_opt_2.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. 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 4. 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 ... 9.165 sec (= 0.153 min) Startup calculation ... 0.946 sec (= 0.016 min) 10.3 % SCF iterations ... 5.154 sec (= 0.086 min) 56.2 % Property calculations ... 0.040 sec (= 0.001 min) 0.4 % SCF Gradient evaluation ... 3.017 sec (= 0.050 min) 32.9 % Geometry relaxation ... 0.009 sec (= 0.000 min) 0.1 % ****ORCA TERMINATED NORMALLY**** TOTAL RUN TIME: 0 days 0 hours 0 minutes 9 seconds 386 msec