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: Thu Jul 9 12:34:19 2026 * Host name: dirac.ttk.pte.hu * Process ID: 1771253 * Working dir.: /home/nora/SU/P6_dlpno *********************************** *************************************** The coordinates will be read from file: water_opt.xyz *************************************** ================================================================================ ----- Orbital basis set information ----- Your calculation utilizes the basis: def2-TZVP F. Weigend and R. Ahlrichs, Phys. Chem. Chem. Phys. 7, 3297 (2005). ----- AuxJ basis set information ----- Your calculation utilizes the AutoAux generation procedure. G. L. Stoychev, A. A. Auer, F. Neese, J. Chem. Theory Comput. 13, 554 (2017) ----- AuxC basis set information ----- Your calculation utilizes the AutoAux generation procedure. G. L. Stoychev, A. A. Auer, F. Neese, J. Chem. Theory Comput. 13, 554 (2017) ----- AuxJK basis set information ----- Your calculation utilizes the AutoAux generation procedure. G. L. Stoychev, A. A. Auer, F. Neese, J. Chem. Theory Comput. 13, 554 (2017) ----- AuxX basis set information ----- Your calculation utilizes the AutoAux generation procedure. G. L. Stoychev, A. A. Auer, F. Neese, J. Chem. Theory Comput. 13, 554 (2017) ================================================================================ WARNINGS Please study these warnings very carefully! ================================================================================ WARNING: Post HF methods need fully converged wavefunctions ===> : Setting SCFConvForced true You can overwrite this default with %scf ConvForced false WARNING: MDCI localization with Augmented Hessian Foster-Boys ===> : Switching off randomization! ================================================================================ INPUT FILE ================================================================================ NAME = water_dlpnoccsdt.inp | 1> ! DLPNO-CCSD(T) def2-TZVP TightSCF TightPNO AutoAux | 2> | 3> * xyzfile 0 1 water_opt.xyz | 4> | 5> | 6> ****END OF INPUT**** ================================================================================ **************************** * Single Point Calculation * **************************** --------------------------------- CARTESIAN COORDINATES (ANGSTROEM) --------------------------------- O 0.000000 0.000000 -0.053501 H 0.765201 0.000000 0.531035 H -0.765201 0.000000 0.531035 ---------------------------- CARTESIAN COORDINATES (A.U.) ---------------------------- NO LB ZA FRAG MASS X Y Z 0 O 8.0000 0 15.999 0.000000 0.000000 -0.101103 1 H 1.0000 0 1.008 1.446020 0.000000 1.003510 2 H 1.0000 0 1.008 -1.446020 0.000000 1.003510 -------------------------------- INTERNAL COORDINATES (ANGSTROEM) -------------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 H 1 0 0 0.962919541172 0.00000000 0.00000000 H 1 2 0 0.962919551813 105.24767459 0.00000000 --------------------------- INTERNAL COORDINATES (A.U.) --------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 H 1 0 0 1.819654221817 0.00000000 0.00000000 H 1 2 0 1.819654241924 105.24767459 0.00000000 --------------------- BASIS SET INFORMATION --------------------- There are 2 groups of distinct atoms Group 1 Type O : 11s6p2d1f contracted to 5s3p2d1f pattern {62111/411/11/1} Group 2 Type H : 5s1p contracted to 3s1p pattern {311/1} 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 : 16s13p12d7f3g contracted to 16s13p12d7f3g pattern {1111111111111111/1111111111111/111111111111/1111111/111} Group 2 Type H : 11s3p1d contracted to 11s3p1d pattern {11111111111/111/1} Atom 0O basis set group => 1 Atom 1H basis set group => 2 Atom 2H basis set group => 2 --------------------------------- AUXILIARY/C BASIS SET INFORMATION --------------------------------- There are 2 groups of distinct atoms Group 1 Type O : 16s13p12d7f3g contracted to 16s13p12d7f3g pattern {1111111111111111/1111111111111/111111111111/1111111/111} Group 2 Type H : 11s3p1d contracted to 11s3p1d pattern {11111111111/111/1} Atom 0O basis set group => 1 Atom 1H basis set group => 2 Atom 2H basis set group => 2 ---------------------------------- AUXILIARY/JK BASIS SET INFORMATION ---------------------------------- There are 2 groups of distinct atoms Group 1 Type O : 16s13p12d7f3g contracted to 16s13p12d7f3g pattern {1111111111111111/1111111111111/111111111111/1111111/111} Group 2 Type H : 11s3p1d contracted to 11s3p1d pattern {11111111111/111/1} Atom 0O basis set group => 1 Atom 1H basis set group => 2 Atom 2H basis set group => 2 --------------------------------- AUXILIARY/X BASIS SET INFORMATION --------------------------------- There are 2 groups of distinct atoms Group 1 Type O : 16s13p12d7f3g contracted to 16s13p12d7f3g pattern {1111111111111111/1111111111111/111111111111/1111111/111} Group 2 Type H : 11s3p1d contracted to 11s3p1d pattern {11111111111/111/1} Atom 0O basis set group => 1 Atom 1H basis set group => 2 Atom 2H basis set group => 2 ------------------------------------------------------------------------------ ORCA STARTUP CALCULATIONS ------------------------------------------------------------------------------ ------------------------------------------------------------------------------ ___ / \ - 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 ... 43 Number of shells ... 19 Maximum angular momentum ... 3 Integral batch strategy ... SHARK/LIBINT Hybrid RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) Printlevel ... 1 Contraction scheme used ... SEGMENTED contraction Prescreening option ... SCHWARTZ Thresh ... 2.500e-11 Tcut ... 2.500e-12 Tpresel ... 2.500e-12 Coulomb Range Separation ... NOT USED Exchange Range Separation ... NOT USED Multipole approximations ... NOT USED Finite Nucleus Model ... NOT USED CABS basis ... NOT available Auxiliary Coulomb fitting basis ... AVAILABLE # of basis functions in Aux-J ... 241 # of shells in Aux-J ... 81 Maximum angular momentum in Aux-J ... 4 Auxiliary J/K fitting basis ... AVAILABLE # of basis functions in Aux-JK ... 241 # of shells in Aux-JK ... 81 Maximum angular momentum in Aux-JK ... 4 Auxiliary Correlation fitting basis ... AVAILABLE # of basis functions in Aux-C ... 241 # of shells in Aux-C ... 81 Maximum angular momentum in Aux-C ... 4 Auxiliary 'external' fitting basis ... NOT available Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 19 => 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 ... 190 Shell pairs after pre-screening ... 190 Total number of primitive shell pairs ... 556 Primitive shell pairs kept ... 535 la=0 lb=0: 66 shell pairs la=1 lb=0: 55 shell pairs la=1 lb=1: 15 shell pairs la=2 lb=0: 22 shell pairs la=2 lb=1: 10 shell pairs la=2 lb=2: 3 shell pairs la=3 lb=0: 11 shell pairs la=3 lb=1: 5 shell pairs la=3 lb=2: 2 shell pairs la=3 lb=3: 1 shell pairs Checking whether 4 symmetric matrices of dimension 43 fit in memory :Max Core in MB = 4096.00 MB in use = 3.56 MB left = 4092.44 MB needed = 0.03 Data fit in memory = YES Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) Calculating RI/JK V-Matrix + Cholesky decomp.... done ( 0.0 sec) Calculating RI/C V-Matrix + Cholesky decomp.... done ( 0.0 sec) Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 9.138656060311 Eh Diagonalization of the overlap matrix: Smallest eigenvalue ... 8.512e-03 Time for diagonalization ... 0.000 sec Threshold for overlap eigenvalues ... 1.000e-07 Number of eigenvalues below threshold ... 0 Time for construction of square roots ... 0.000 sec Total time needed ... 0.001 sec ------------------- DFT GRID GENERATION ------------------- General Integration Accuracy IntAcc ... 4.388 Radial Grid Type RadialGrid ... OptM3 with GC (2021) Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) Angular grid pruning method GridPruning ... 4 (adaptive) Weight generation scheme WeightScheme... mBecke (2022) Basis function cutoff BFCut ... 1.0000e-11 Integration weight cutoff WCut ... 1.0000e-14 Partially contracted basis set ... off Rotationally invariant grid construction ... off Angular grids for H and He will be reduced by one unit Total number of grid points ... 12756 Total number of batches ... 201 Average number of points per batch ... 63 Average number of grid points per atom ... 4252 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: 14.0 MB ------------------------------------------------------------------------------- ORCA GUESS Start orbitals & Density for SCF / CASSCF ------------------------------------------------------------------------------- ------------ SCF SETTINGS ------------ Hamiltonian: Ab initio Hamiltonian Method .... Hartree-Fock(GTOs) General Settings: Integral files IntName .... water_dlpnoccsdt Hartree-Fock type HFTyp .... RHF Total Charge Charge .... 0 Multiplicity Mult .... 1 Number of Electrons NEL .... 10 Basis Dimension Dim .... 43 Nuclear Repulsion ENuc .... 9.1386560603 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 .... 1 Energy Change TolE .... 1.000e-08 Eh 1-El. energy change .... 1.000e-05 Eh Orbital Gradient TolG .... 1.000e-05 Orbital Rotation angle TolX .... 1.000e-05 DIIS Error TolErr .... 5.000e-07 ------------------------------ INITIAL GUESS: 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) 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_dlpnoccsdt.en.tmp) **** Finished Guess after 0.0 sec Maximum memory used throughout the entire GUESS-calculation: 7.3 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 -75.9556057178493802 0.00e+00 3.51e-03 4.37e-02 3.47e-01 0.700 0.1 2 -75.9966717401059952 -4.11e-02 2.41e-03 2.86e-02 2.15e-01 0.700 0.0 ***Turning on AO-DIIS*** 3 -76.0180388808279588 -2.14e-02 9.26e-04 1.25e-02 1.64e-01 0.700 0.0 4 -76.0308441133001622 -1.28e-02 5.71e-04 8.30e-03 1.16e-01 0.700 0.0 5 -76.0393514400830099 -8.51e-03 4.17e-04 6.13e-03 8.10e-02 0.700 0.0 6 -76.0452136285115046 -5.86e-03 1.05e-03 1.54e-02 5.67e-02 0.000 0.0 *** Initializing SOSCF *** ---------------------------------------S-O-S-C-F-------------------------------------- Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) -------------------------------------------------------------------------------------- 7 -76.0586524046193517 -1.34e-02 1.10e-04 9.39e-04 2.87e-03 0.0 *** Restarting incremental Fock matrix formation *** 8 -76.0586652794217173 -1.29e-05 6.76e-05 5.36e-04 5.10e-04 0.0 9 -76.0586681619298304 -2.88e-06 5.42e-05 6.08e-04 2.73e-04 0.0 10 -76.0586688049087627 -6.43e-07 6.98e-06 8.12e-05 7.42e-05 0.0 11 -76.0586688352930764 -3.04e-08 2.18e-06 2.23e-05 3.09e-05 0.0 12 -76.0586688394669466 -4.17e-09 4.74e-07 5.03e-06 3.43e-06 0.0 **** Energy Check signals convergence **** ***************************************************** * SUCCESS * * SCF CONVERGED AFTER 12 CYCLES * ***************************************************** **** ENERGY FILE WAS UPDATED (water_dlpnoccsdt.en.tmp) **** ---------------- TOTAL SCF ENERGY ---------------- Total Energy : -76.05866883961343 Eh -2069.66160 eV Components: Nuclear Repulsion : 9.13865606031082 Eh 248.67547 eV Electronic Energy : -85.19732489992425 Eh -2318.33707 eV One Electron Energy: -122.98284091674391 Eh -3346.53324 eV Two Electron Energy: 37.78551601681966 Eh 1028.19616 eV Virial components: Potential Energy : -152.03889562595293 Eh -4137.18868 eV Kinetic Energy : 75.98022678633949 Eh 2067.52708 eV Virial Ratio : 2.00103240088365 --------------- SCF CONVERGENCE --------------- Last Energy change ... 4.1739e-09 Tolerance : 1.0000e-08 Last MAX-Density change ... 5.0261e-06 Tolerance : 1.0000e-07 Last RMS-Density change ... 4.7421e-07 Tolerance : 5.0000e-09 Last DIIS Error ... 2.8664e-03 Tolerance : 5.0000e-07 Last Orbital Gradient ... 3.4334e-06 Tolerance : 1.0000e-05 Last Orbital Rotation ... 3.6803e-06 Tolerance : 1.0000e-05 ---------------- ORBITAL ENERGIES ---------------- NO OCC E(Eh) E(eV) 0 2.0000 -20.560402 -559.4770 1 2.0000 -1.346293 -36.6345 2 2.0000 -0.713078 -19.4039 3 2.0000 -0.578776 -15.7493 4 2.0000 -0.507355 -13.8058 5 0.0000 0.127217 3.4618 6 0.0000 0.196805 5.3553 7 0.0000 0.523569 14.2470 8 0.0000 0.564756 15.3678 9 0.0000 0.597479 16.2582 10 0.0000 0.638316 17.3695 11 0.0000 0.768436 20.9102 12 0.0000 0.772492 21.0206 13 0.0000 1.416712 38.5507 14 0.0000 1.438303 39.1382 15 0.0000 1.552991 42.2590 *Only the first 10 virtual orbitals were printed. ******************************** * MULLIKEN POPULATION ANALYSIS * ******************************** ----------------------- MULLIKEN ATOMIC CHARGES ----------------------- 0 O : -0.691443 1 H : 0.345722 2 H : 0.345722 Sum of atomic charges: -0.0000000 -------------------------------- MULLIKEN REDUCED ORBITAL CHARGES -------------------------------- 0 O s : 3.808145 s : 3.808145 pz : 1.606705 p : 4.855561 px : 1.282562 py : 1.966294 dz2 : 0.002855 d : 0.026129 dxz : 0.018232 dyz : 0.002298 dx2y2 : 0.002745 dxy : 0.000000 f0 : 0.000062 f : 0.001607 f+1 : 0.000114 f-1 : 0.000019 f+2 : 0.000824 f-2 : 0.000000 f+3 : 0.000451 f-3 : 0.000137 1 H s : 0.608508 s : 0.608508 pz : 0.013905 p : 0.045771 px : 0.016240 py : 0.015626 2 H s : 0.608508 s : 0.608508 pz : 0.013905 p : 0.045771 px : 0.016240 py : 0.015626 ******************************* * LOEWDIN POPULATION ANALYSIS * ******************************* ---------------------- LOEWDIN ATOMIC CHARGES ---------------------- 0 O : -0.319416 1 H : 0.159708 2 H : 0.159708 ------------------------------- LOEWDIN REDUCED ORBITAL CHARGES ------------------------------- 0 O s : 3.460325 s : 3.460325 pz : 1.622856 p : 4.822859 px : 1.293672 py : 1.906331 dz2 : 0.001205 d : 0.033921 dxz : 0.026264 dyz : 0.000753 dx2y2 : 0.005699 dxy : 0.000000 f0 : 0.000215 f : 0.002312 f+1 : 0.000480 f-1 : 0.000000 f+2 : 0.001125 f-2 : 0.000000 f+3 : 0.000492 f-3 : 0.000000 1 H s : 0.678885 s : 0.678885 pz : 0.055768 p : 0.161407 px : 0.059181 py : 0.046458 2 H s : 0.678885 s : 0.678885 pz : 0.055768 p : 0.161407 px : 0.059181 py : 0.046458 ***************************** * 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 8.6914 8.0000 -0.6914 1.7808 1.7808 -0.0000 1 H 0.6543 1.0000 0.3457 0.8952 0.8952 -0.0000 2 H 0.6543 1.0000 0.3457 0.8952 0.8952 -0.0000 Mayer bond orders larger than 0.100000 B( 0-O , 1-H ) : 0.8904 B( 0-O , 2-H ) : 0.8904 ------- TIMINGS ------- Total SCF time: 0 days 0 hours 0 min 0 sec Total time .... 0.377 sec Sum of individual times .... 0.349 sec ( 92.7%) SCF preparation .... 0.026 sec ( 6.8%) Fock matrix formation .... 0.314 sec ( 83.4%) Startup .... 0.000 sec ( 0.1% of F) Coulomb+Exchange Fock .... 0.330 sec (104.9% of F) Diagonalization .... 0.000 sec ( 0.0%) Density matrix formation .... 0.002 sec ( 0.4%) Total Energy calculation .... 0.000 sec ( 0.1%) Population analysis .... 0.001 sec ( 0.2%) Orbital Transformation .... 0.001 sec ( 0.2%) Orbital Orthonormalization .... 0.000 sec ( 0.0%) DIIS solution .... 0.004 sec ( 1.0%) SOSCF solution .... 0.002 sec ( 0.5%) Finished LeanSCF after 0.4 sec Maximum memory used throughout the entire LEANSCF-calculation: 13.0 MB ------------------------------------------------------------------------------ ORCA PROPERTY INTEGRAL CALCULATIONS ------------------------------------------------------------------------------ GBWName ... water_dlpnoccsdt.gbw Number of atoms ... 3 Number of basis functions ... 43 Max core memory ... 4096 MB Dipole integrals ... YES Quadrupole integrals ... NO Linear momentum integrals ... YES Angular momentum integrals ... YES Higher moments length integrals ... NO Higher moments velocity integrals ... NO Kinetic energy integrals ... NO GIAO right hand sides ... NO GIAO dipole derivative integrals ... NO SOC integrals ... NO EPR diamagnetic integrals (GIAO) ... NO EPR gauge integrals ... NO Field gradient integrals ... NO ( 0 nuclei) Spin-dipole/Fermi contact integrals ... NO ( 0 nuclei) Contact density integrals ... NO ( 0 nuclei) Nucleus-orbit integrals ... NO ( 0 nuclei) Geometric perturbations ... NO ( 3 nuclei) Choice of electric origin ... Center of mass Position of electric origin ... ( 0.0000, 0.0000, 0.0225) Choice of magnetic origin ... GIAO Position of magnetic origin ... ( 0.0000, 0.0000, 0.0000) Calculating integrals ... Electric Dipole (Length) done ( 0.0 sec) Calculating integrals ... Linear Momentum done ( 0.0 sec) Calculating integrals ... Angular Momentum (ElOri) done ( 0.0 sec) Property integrals calculated in 0.0 sec Maximum memory used throughout the entire PROPINT-calculation: 7.4 MB -------------------------------------------------------------------------------- ORCA-MATRIX DRIVEN CI -------------------------------------------------------------------------------- Wavefunction type ----------------- Correlation treatment ... CCSD Single excitations ... ON Orbital optimization ... OFF Calculation of Z vector ... OFF Calculation of Brueckner orbitals ... OFF Perturbative triple excitations ... ON Calculation of F12 correction ... OFF Frozen core treatment ... chemical core (2 el) Reference Wavefunction ... RHF Internal Orbitals: 1 ... 4 ( 4 MO's/ 8 electrons) Virtual Orbitals: 5 ... 42 ( 38 MO's ) Number of AO's ... 43 Number of electrons ... 10 Number of correlated electrons ... 8 Algorithmic settings -------------------- Integral transformation ... All integrals via the RI transformation K(C) Formation ... RI-DLPNO PNO-Integral Storage ... ON DISK PNO occupation number cut-off ... 1.000e-07 Singles PNO occupation number cut-off ... 3.000e-09 PNO Mulliken prescreening cut-off ... 1.000e-03 Domain cut-off (Mulliken population) ... 1.000e-03 PNO Normalization ... 1 Maximum number of iterations ... 50 Convergence tolerance (max. residuum) ... 1.000e-05 Level shift for amplitude update ... 2.000e-01 Maximum number of DIIS vectors ... 7 DIIS turned on at iteration ... 0 Damping before turning on DIIS ... 0.500 Damping after turning on DIIS ... 0.000 Pair specific amplitude update ... OFF Natural orbital iterations ... OFF Perturbative natural orbital generation ... OFF Printlevel ... 2 Singles Fock matrix elements calculated using PNOs. Memory handling: ---------------- Maximum memory for working arrays ... 4096 MB Data storage in matrix containers ... UNCOMPRESSED Data type for integral storage ... DOUBLE In-Core Storage of quantities: Amplitudes+Sigma Vector ... NO J+K operators ... NO DIIS vectors ... NO 3-external integrals ... NO 4-external integrals ... NO Localization treatment: ----------------------- Localization option ... 6 Localization threshhold ... -1.0e+00 Using relative localization threshhold ... 1.0e-08 Neglect threshold for strong pairs ... 1.000e-05 Eh Prescreening threshold for very weak pairs ... 1.000e-07 Eh Initializing the integral package ... done Localizing the valence orbitals Localizing the valence orbitals ------------------------------------------------------------------------------ ORCA ORBITAL LOCALIZATION ------------------------------------------------------------------------------ Input orbitals are from ... water_dlpnoccsdt.gbw Output orbitals are to ... water_dlpnoccsdt.loc Max. number of iterations ... 128 Localizations seeded randomly ... off Convergence tolerance ... 1.000e-06 Using relative localization threshhold ... 1.000e-08 Threshold for strong local MOs ... 9.500e-01 Threshold for bond MOs ... 8.500e-01 Operator ... 0 Orbital range for localization ... 1 to 4 Localization criterion ... FOSTER-BOYS (AUGMENTED HESSIAN) Doing the dipole integrals ... o.k. Initial value of the localization sum : 0.290972 ITERATION 0 : L= 2.4088963915 DL= 2.12e+00 (AVERGE_DL)= 0.5941273706 ITERATION 1 : L= 2.4752625646 DL= 6.64e-02 (AVERGE_DL)= 0.1051714260 ITERATION 2 : L= 2.4875242494 DL= 1.23e-02 (AVERGE_DL)= 0.0452063507 ITERATION 3 : L= 2.4891939801 DL= 1.67e-03 (AVERGE_DL)= 0.0166819799 ITERATION 4 : L= 2.4893218592 DL= 1.28e-04 (AVERGE_DL)= 0.0046166190 ITERATION 5 : L= 2.4893341626 DL= 1.23e-05 (AVERGE_DL)= 0.0014319812 ITERATION 6 : L= 2.4893352282 DL= 1.07e-06 (AVERGE_DL)= 0.0004214233 ITERATION 7 : L= 2.4893353214 DL= 9.32e-08 (AVERGE_DL)= 0.0001246413 LOCALIZATION SUM CONVERGED ------------------------------------------------------ AUGMENTED HESSIAN OPTIMIZATION OF FOSTER-BOYS ORBITALS ------------------------------------------------------ Spin operator: 0 Orbital window: 1 to 4 Number of iterations: 128 Gradient tolerance: 1.000e-06 Number of pairs: 6 Davidson threshold: 2000 Diagonalization method: LAPACK Iter: 0 L: 2.4893353214 Grad. norm: 1.765631e-04 *** Likely close to a maximum now. *** Augmented Hessian eigenvalues: 1.74e-08 -1.36e+00 -3.37e+00 -4.90e+00 ... Iter: 1 L: 2.4893353301 Grad. norm: 8.247844e-09 LOCALIZATION HAS CONVERGED. Eigenvalues of the Hessian: 0 -1.357e+00 1 -3.370e+00 2 -4.900e+00 3 -5.454e+00 4 -7.340e+00 5 -9.793e+00 -------------------------------------------------------------------------------- LOCALIZED MOLECULAR ORBITAL COMPOSITIONS -------------------------------------------------------------------------------- The Mulliken populations for each LMO on each atom are computed The LMO`s will be ordered according to atom index and type (A) Strongly localized MO`s have populations of >=0.950 on one atom (B) Two center bond orbitals have populations of >=0.850 on two atoms (C) Other MO`s are considered to be `delocalized` FOUND - 2 strongly local MO`s - 2 two center bond MO`s - 0 significantly delocalized MO`s Rather strongly localized orbitals: MO 2: 0O - 1.004915 MO 1: 0O - 1.004915 Bond-like localized orbitals: MO 4: 2H - 0.337944 and 0O - 0.667987 MO 3: 1H - 0.337944 and 0O - 0.667987 Localized MO's were stored in: water_dlpnoccsdt.loc Localizing the core orbitals ------------------------------------------------------------------------------ ORCA ORBITAL LOCALIZATION ------------------------------------------------------------------------------ Input orbitals are from ... water_dlpnoccsdt.loc Output orbitals are to ... water_dlpnoccsdt.loc Max. number of iterations ... 128 Localizations seeded randomly ... off Convergence tolerance ... 1.000e-06 Using relative localization threshhold ... 1.000e-08 Threshold for strong local MOs ... 9.500e-01 Threshold for bond MOs ... 8.500e-01 Operator ... 0 Orbital range for localization ... 0 to 0 Localization criterion ... FOSTER-BOYS (AUGMENTED HESSIAN) Doing the dipole integrals ... o.k. ORCA_LOC: ONLY ONE ORBITAL - SKIPPING LOCALIZATION -------------------------------------------------------------------------------- LOCALIZED MOLECULAR ORBITAL COMPOSITIONS -------------------------------------------------------------------------------- The Mulliken populations for each LMO on each atom are computed The LMO`s will be ordered according to atom index and type (A) Strongly localized MO`s have populations of >=0.950 on one atom (B) Two center bond orbitals have populations of >=0.850 on two atoms (C) Other MO`s are considered to be `delocalized` FOUND - 1 strongly local MO`s - 0 two center bond MO`s - 0 significantly delocalized MO`s Rather strongly localized orbitals: MO 0: 0O - 0.999917 Localized MO's were stored in: water_dlpnoccsdt.loc Warning: reference - re-canonicalizations have been set to INT 1 VIRT 1 Warning: internal orbitals are localized - no re-canonicalization of internal orbitals Warning: UsePNO is turned on - no re-canonicalization of internal and virtual orbitals Fock densities were made Making Fock matrix and reference energy: -------------------------- CLOSED-SHELL FOCK OPERATOR -------------------------- Time needed for Fock operator ... 0.026 sec Reference energy ... -76.058668840 -------------- DLPNO SETTINGS (2015 fully linear scaling implementation) -------------- TCutMKN: 1.000e-03 TCutPAO: 1.000e-03 TCutPNO: 1.000e-07 TCutPNOSingles: 3.000e-09 TCutEN: 9.700e-01 TCutPAOExt: 1.000e-01 TCutPairs: 1.000e-05 TCutPre: 1.000e-07 TCutOSV: 1.000e-06 TCutDOij: 1.000e-05 TCutDO: 5.000e-03 TCutC: 1.000e-04 TCutCPAO: 1.000e-03 TCutCMO: 1.000e-03 TScaleDOMP2PreScr: 2.000e+00 TScaleMKNMP2PreScr:1.000e+01 TScalePNOMP2PreScr:1.000e+00 PAO overlap thresh 1.000e-08 Using PNOs for Singles Fock computation Use new domains Use fully linear algorithm TCutTNO: 1.000e-09 TCutMP2Pairs: 1.000e-06 TCutDOStrong: 1.000e-02 TCutDOWeak: 2.000e-02 TCutMKNStrong: 1.000e-02 TCutMKNWeak: 1.000e-01 NTCutTNO: 1 -------------------------- Mulliken population of the LMOs ... ok Performing proximity check ... No problems found Calculating differential overlap integrals ... ok -------------------------- ELECTRON PAIR PRESCREENING -------------------------- Dipole-based pair screening .... used TCutDOij = 1.000000e-05 TCutPre = 1.000000e-07 .... Finished loop over pairs Total time spent in the prescreening ... 0.000 sec sum of pair energies estimated for screened out pairs ... 0.000000000000 Eh Thresholds for map construction and integral transformation for crude MP2: TCutMKN ... 1.0e-02 TCutDO ... 1.0e-02 TCutPairs ... 1.0e-05 TCutPNO_CrudeMP2 ... 1.0e-07 TCutPNOSingles_CrudeMP2 ... 3.0e-09 -------------------------------- LOCAL RI TRANSFORMATION (IAVPAO) -------------------------------- Orbital window: 1 to 4 Number of PAOs: 43 Basis functions: 43 (19 shells) Aux. functions: 241 (81 shells) Use SHARK: on Have SHARK: yes Processing maps (0.0 sec) Average map sizes: Aux shells -> MOs 4.0 Aux shells -> PAOs 43.0 MOs -> AO shells 19.0 PAOs -> AO shells 19.0 Calculating integrals (0.0 sec, 0.319 MB) Sorting integrals (0.0 sec, 0.316 MB) Total time for the integral transformation: 0.0 sec -------------------------------- INITIAL GUESS AND PNO GENERATION -------------------------------- PNO truncation parameters .... PAOOverlapThresh = 1.000e-08 TCutPairs = 1.000e-05 TCutPNO = 1.000e-07 TCutPNOSingles = 3.000e-09 TCutMP2Pairs = 1.000e-06 TCutMKN = 1.000e-02 TCutDO = 1.000e-02 Pair selection .... not used Type of local MP2 treatment .... semi-local MP2 Strategy for PNO selection .... occupation number selection Pair density normalization .... MP2 norm Spin component scaling .... not used .... Finished loop over pairs Making pair pair interaction lists ... done =========================== 10 OF 10 PAIRS ARE KEPT CCSD PAIRS 0 OF 10 PAIRS ARE KEPT MP2 PAIRS FOR (T) 0 OF 10 PAIRS ARE SKIPPED =========================== Total time spent in the initial guess ... 0.033 sec SL-MP2 correlation energy (all non-screened pairs) ... -0.247017841454 Eh Initial PNO correlation energy ... -0.246984546206 Eh sum of pair energies prescreened and skipped MP2 pairs... 0.000000000000 Eh sum of pair energies of crude MP2 skipped pairs only ... 0.000000000000 Eh sum of MP2 pair energies for pairs that were not kept ... 0.000000000000 Eh sum of PNO error estimates for the kept pairs ... -0.000033295247 Eh -------------------- sum of all corrections -0.000033295247 Initial total correlation energy -0.247017841454 Thresholds for map construction and integral transformation for fine MP2 and CCSD(T) calculation: TCutMKN ... 1.0e-03 TCutDO ... 5.0e-03 TCutPairs ... 1.0e-05 TCutCMO ... 1.0e-03 TCutCPAO ... 1.0e-03 Thresholds for map construction and integral transformation for strong Triples: TCutMKN ... 1.0e-02 TCutDO ... 1.0e-02 TCutCMO ... 1.0e-03 TCutCPAO ... 1.0e-03 Thresholds for map construction and integral transformation for weak Triples: TCutMKN ... 1.0e-01 TCutDO ... 2.0e-02 TCutCMO ... 1.0e-03 TCutCPAO ... 1.0e-03 -------------------------------- LOCAL RI TRANSFORMATION (IAVPAO) -------------------------------- Orbital window: 1 to 4 Number of PAOs: 43 Basis functions: 43 (19 shells) Aux. functions: 241 (81 shells) Use SHARK: on Have SHARK: yes Processing maps (0.0 sec) Average map sizes: Aux shells -> MOs 4.0 Aux shells -> PAOs 43.0 MOs -> AO shells 19.0 PAOs -> AO shells 19.0 Calculating integrals (0.0 sec, 0.319 MB) Sorting integrals (0.0 sec, 0.316 MB) Total time for the integral transformation: 0.0 sec -------------------------------- INITIAL GUESS AND PNO GENERATION -------------------------------- PNO truncation parameters .... ScaleTCutPNO = 1.000e-02 PAOOverlapThresh = 1.000e-08 TCutPairs = 1.000e-05 TCutPNO = 1.000e-07 TCutPNOSingles = 3.000e-09 TCutMP2Pairs = 1.000e-06 TCutMKN = 1.000e-03 TCutDO = 5.000e-03 Pair selection .... not used Type of local MP2 treatment .... full local MP2 Strategy for PNO selection .... occupation number selection Pair density normalization .... MP2 norm Spin component scaling .... not used PASS-1: Formation of initial guess LMP2 amplitudes Initial amplitudes guess done. Entering LMP2 iteration loop: Max. no of iterations ... 50 Energy convergence tolerance ... 1.0e-07 Residual convergence tolerance ... 5.0e-07 Fock matrix cutoff ... 1.0e-05 Eh DIIS convergence acceleration parameters: Max # vectors in DIIS ... 7 Start iteration of DIIS ... 0 Levelshift ... 2.000e-01 Damping factor 1 ... 5.000e-01 Damping factor 2 ... 1.000e+00 L-MP2 PNO cut-off ... 1.0e-09 L-MP2 PNO cut-off (core) ... 1.0e-11 *** Turning on DIIS *** LMP2-Iter= 0: ELMP2= -0.251514572478 DE= 4.5e-03 RMAX= 8.5e-03 LMP2-Iter= 1: ELMP2= -0.253984462970 DE= 2.5e-03 RMAX= 2.0e-03 LMP2-Iter= 2: ELMP2= -0.254326762359 DE= 3.4e-04 RMAX= 4.7e-04 LMP2-Iter= 3: ELMP2= -0.254368779322 DE= 4.2e-05 RMAX= 1.5e-04 LMP2-Iter= 4: ELMP2= -0.254372082750 DE= 3.3e-06 RMAX= 2.4e-05 LMP2-Iter= 5: ELMP2= -0.254372058466 DE= 2.4e-08 RMAX= 7.1e-06 LMP2-Iter= 6: ELMP2= -0.254372025326 DE= 3.3e-08 RMAX= 5.7e-07 LMP2-Iter= 7: ELMP2= -0.254372021036 DE= 4.3e-09 RMAX= 2.3e-07 => CONVERGED PASS-2: Formation of Pair natural orbitals .... Finished loop over pairs PNO Occupation Number Statistics: | Av. % of trace(Dij) retained ... 99.998818848976 | sigma^2 in % of trace(Dij) retained ... 5.81e-07 | Av. % of trace(Di) retained ... 100.000000000000 | sigma^2 in % of trace(Di) retained ... 9.09e-28 Distributions of % trace(Dij) recovered: | >= 99.9 ... 10 (100.0 % of all pairs) Distributions of % trace(Di) recovered : | >= 99.9 ... 4 (100.0 % of all I-pairs ) Making pair pair interaction lists ... done =========================== 10 OF 10 PAIRS ARE KEPT =========================== Total time spent in the initial guess ... 0.051 sec L-MP2 correlation energy (all non-screened pairs) ... -0.254372021036 Eh L-MP2 PNO error correction ... 0.000000000000 Eh -------------------- Initial total L-MP2 energy (non-screened pairs) ... -0.254372021036 Eh Initial PNO correlation energy ... -0.254342220787 Eh sum of pair energies estimated for screened out pairs ... 0.000000000000 Eh sum of MP2 pair energies for pairs that were not kept ... 0.000000000000 Eh sum of PNO error estimates for the kept pairs ... -0.000029800248 Eh -------------------- sum of all corrections -0.000029800248 Initial total correlation energy -0.254372021036 Thresholds for map construction and integral transformation for fine MP2 and CCSD(T) calculation: TCutMKN ... 1.0e-03 TCutDO ... 5.0e-03 TCutPairs ... 1.0e-05 TCutCMO ... 1.0e-03 TCutCPAO ... 1.0e-03 Time for aux screen maps: 0.000 Time for maps after fine MP2: 0.000 ----------------------------- LOCAL RI TRANSFORMATION (IJV) ----------------------------- Orbital window: 1 to 4 Basis functions: 43 (19 shells) Aux. functions: 241 (81 shells) Use SHARK: on Processing maps (0.0 sec) Average map sizes: Aux shells -> MOs(i) 4.0 Aux shells -> MOs(j) 4.0 MOs -> AO shells 19.0 Calculating integrals (0.0 sec, 0.032 MB) Sorting integrals (0.0 sec, 0.029 MB) Total time for the integral transformation: 0.0 sec -------------------------------- LOCAL RI TRANSFORMATION (VABPAO) -------------------------------- Number of PAOs: 43 Basis functions: 43 (19 shells) Aux. functions: 241 (81 shells) Use SHARK: on Processing maps (0.0 sec) Average map sizes: Aux shells -> PAOs 43.0 PAOs -> AO shells 19.0 Calculating integrals (0.0 sec, 3.402 MB) Finished ------------------------------------- Pair Pair Term precalculation with RI-(ij|mn) and (im|jn) transformation ON THE FLY ------------------------------------- IBatch 1 (of 1) ... done ( 0.269 sec) Total EXT ... 0.269 sec IAVPA Available = YES VABPAO Available= YES IJV Available = YES IJK Available = NO PNO3i Available = YES PNO3j Available = YES PNO4 Available = YES --------------------- RI-PNO TRANSFORMATION --------------------- Total Number of PNOs ... 354 Average number of PNOs per pair ... 35 Maximal number of PNOs per pair ... 37 #pairs with 1 - 5 PNOs : 0 #pairs with 6 - 10 PNOs : 0 #pairs with 11 - 15 PNOs : 0 #pairs with 16 - 20 PNOs : 0 #pairs with 21 - 25 PNOs : 0 #pairs with 26 - 30 PNOs : 0 #pairs with 31 - 35 PNOs : 3 #pairs with 36 - 40 PNOs : 7 #pairs with 41 - 45 PNOs : 0 #pairs with 46 - 50 PNOs : 0 Generation of (ij|ab)[P] integrals ... on Generation of (ia|bc)[P],(ja|bc)[P] integrals ... on Storage of 3 and 4 external integrals ... on Generation of ALL (ka|bc)[P] integrals ... on Keep RI integrals in memory ... off Ibatch: 1 (of 1) Starting 2-4 index PNO integral generation ... done Timings: Total PNO integral transformation time ... 0.165 sec Size of the 3-external file ... 3 MB Size of the 4-external file ... 15 MB Size of the IKJL file ... 0 MB Size of the all 3-external file ... 6 MB Size of the 1-external file ... 0 MB Making pair/pair overlap matrices ... done ( 0.002 sec) Size of the pair overlap file ... 1 MB Redoing the guess amplitudes ... done ( 0.000 sec) ------------------------- FINAL STARTUP INFORMATION ------------------------- E(0) ... -76.058668840 E(L-MP2) ... -0.254372021 E(L-MP2) including corrections ... -0.254372021 Initial E(tot) ... -76.313040861 ... 0.054731053 Number of pairs included ... 10 Total number of pairs ... 10 ------------------------------------------------ RHF COUPLED CLUSTER ITERATIONS ------------------------------------------------ Number of PNO amplitudes to be optimized ... 12548 Number of non-PNO amplitudes ... 14440 Untruncated number of regular amplitudes ... 14440 Iter E(tot) E(Corr) Delta-E Residual Time 0 -76.305694338 -0.246995698 0.007376323 0.016622974 0.28 *** Turning on DIIS *** 1 -76.312812013 -0.254113373 -0.007117675 0.004751368 0.28 2 -76.318483623 -0.259784983 -0.005671611 0.001445962 0.28 3 -76.319456315 -0.260757675 -0.000972691 0.000862855 0.28 4 -76.319698798 -0.261000158 -0.000242483 0.000201193 0.28 5 -76.319747484 -0.261048844 -0.000048686 0.000125612 0.28 6 -76.319756516 -0.261057876 -0.000009032 0.000051709 0.28 7 -76.319757374 -0.261058734 -0.000000858 0.000026921 0.28 8 -76.319758198 -0.261059558 -0.000000824 0.000007603 0.28 --- The Coupled-Cluster iterations have converged --- ---------------------- COUPLED CLUSTER ENERGY ---------------------- E(0) ... -76.058668840 E(CORR)(strong-pairs) ... -0.261059558 E(CORR)(weak-pairs) ... -0.000029800 E(CORR)(corrected) ... -0.261089358 E(TOT) ... -76.319758198 Singles Norm **1/2 ... 0.020299607 T1 diagnostic ... 0.007176995 ------------------ LARGEST AMPLITUDES ------------------ 1-> 9 1-> 9 0.024547 2-> 9 2-> 9 0.024547 4-> 5 4-> 5 0.023827 3-> 5 3-> 5 0.023827 4-> 7 4-> 7 0.023458 3-> 7 3-> 7 0.023458 4-> 10 4-> 10 0.022248 3-> 10 3-> 10 0.022248 4-> 13 4-> 13 0.019796 3-> 13 3-> 13 0.019796 3-> 11 3-> 11 0.019498 4-> 11 4-> 11 0.019498 4-> 10 4-> 5 0.019490 4-> 5 4-> 10 0.019490 3-> 10 3-> 5 0.019490 3-> 5 3-> 10 0.019490 ------------------------------------------- DLPNO BASED TRIPLES CORRECTION ------------------------------------------- Singles multiplier ... 1.000000 TCutTNO ... 1.000e-09 TCutMP2Pairs ... 1.000e-06 TCutDOStrong ... 1.000e-02 TCutMKNStrong ... 1.000e-02 TCutDOWeak ... 2.000e-02 TCutMKNWeak ... 1.000e-01 Fragment selection .... not used Fock matrix occ-virt block is zero --> Setting DT_in_Triples to false. Number of Triples that are to be computed ... 16 . . . . . . . . . 10% done 20% done 30% done 40% done 50% done 60% done 70% done 80% done 90% done ( 0.115 sec) Triples timings: Total time for T0 ... 0.126 sec Total time for Iterative (T) ... 0.000 sec Total time of overall (T) ... 0.126 sec Triples List generation ... 0.000 sec TNO generation ... 0.010 sec Pair density generation ... 0.000 sec Look up tables ... 0.000 sec Generating 3-index integrals ... 0.035 sec Make 4-ind.int. from 3-ind.int... 0.048 sec Projecting amplitudes (D + S) ... 0.002 sec Downprojecting integrals ... 0.000 sec Energy contr. (sum over a,b,c)... 0.011 sec Fitting ET(->0) ... 0.000 sec Everything after 3-index ... 0.080 sec Timing details: TNO integrals ... 0.079 sec Reading 3-index integrals ... 0.001 sec Sorting integrals ... 0.011 sec Sorting integrals 1 ... 0.000 sec Sorting integrals 2 ... 0.004 sec Sorting integrals 3 ... 0.001 sec Sorting integrals 4 ... 0.000 sec Sorting integrals 5 ... 0.000 sec Sorting integrals 6 ... 0.005 sec Calculating local VM**-1/2 ... 0.006 sec Orthogonal. integrals ... 0.014 sec Multipl. 3-index integrals ... 0.048 sec All concerning IRIab (w/TNO) ... 0.022 sec Calculate W0/W1 ... 0.018 sec W 3-ext contribution ... 0.012 sec W 3-int contribution ... 0.001 sec Sorting W ... 0.004 sec V exchange contribution ... 0.004 sec Timings for Triples without generation of 3-index integrals ... 0.080 sec 0 weak pairs ... 0.080 sec 1 weak pair ... 0.000 sec 2 weak pairs ... 0.000 sec 3 weak pairs ... 0.000 sec Extra time for extrapolation ... 0.000 sec Number of Triples (0, 1, 2, 3 weak pairs; overall): 16 0 0 0 ( 16) Number of Atoms (0, 1, 2, 3 weak pairs; overall): 3.0 0.0 0.0 0.0 ( 3) Number of PAOs (0, 1, 2, 3 weak pairs; overall): 43.0 0.0 0.0 0.0 ( 43) Number of AuxFcns (0, 1, 2, 3 weak pairs; overall): 219.1 0.0 0.0 0.0 ( 241) Number of TNOs (0, 1, 2, 3 weak pairs ): 38.0 0.0 0.0 0.0 Aver. Number of NTNO, Atoms, PAOs, AuxFcns / Triples: 16 38.0 3.0 43.0 219.1 Triples Correction (T) ... -0.006739916 Final correlation energy ... -0.267829274 E(CCSD) ... -76.319758198 E(CCSD(T)) ... -76.326498114 -------------------------------------------------------------------------------- TIMINGS -------------------------------------------------------------------------------- Total execution time ... 3.568 sec Localization of occupied MO's ... 0.059 sec ( 1.7%) Fock Matrix Formation ... 0.026 sec ( 0.7%) Global overlap, Fock, MKN matrices ... 0.075 sec ( 2.1%) Differential overlap integrals ... 0.038 sec ( 1.1%) Organizing maps ... 0.000 sec ( 0.0%) RI 3-index integral generations ... 0.082 sec ( 2.3%) RI-PNO integral transformation ... 0.469 sec ( 13.1%) Initial Guess ... 0.085 sec ( 2.4%) DIIS Solver ... 0.011 sec ( 0.3%) State Vector Update ... 0.000 sec ( 0.0%) Sigma-vector construction ... 2.509 sec ( 70.3%) (0-ext) ... 0.020 sec ( 0.8% of sigma) (2-ext Fock) ... 0.003 sec ( 0.1% of sigma) (2-ext) ... 0.057 sec ( 2.3% of sigma) (4-ext) ... 0.580 sec ( 23.1% of sigma) (4-ext-corr) ... 1.663 sec ( 66.3% of sigma) CCSD doubles correction ... 0.005 sec ( 0.2% of sigma) ... 0.011 sec ( 0.4% of sigma) (1-ext) ... 0.005 sec ( 0.2% of sigma) (3-ext) ... 0.028 sec ( 1.1% of sigma) Fock-dressing ... 0.083 sec ( 3.3% of sigma) Singles amplitudes ... 0.001 sec ( 0.0% of sigma) (ik|jl)-dressing ... 0.010 sec ( 0.4% of sigma) (ij|ab),(ia|jb)-dressing ... 0.037 sec ( 1.5% of sigma) Total Time for computing (T) ... 0.126 sec ( 3.5% of ALL) Maximum memory used throughout the entire MDCI-calculation: 214.5 MB ------------------------- -------------------- FINAL SINGLE POINT ENERGY -76.326498113918 ------------------------- -------------------- ------------------------------------------------------------------------------ ORCA PROPERTY CALCULATIONS ------------------------------------------------------------------------------ GBWName ... water_dlpnoccsdt.gbw Number of atoms ... 3 Number of basis functions ... 43 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 ... 0.000000 0.000000 0.022511 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 : -76.0586688396134321 Eh Basis : AO X Y Z Electronic contribution: 0.000000004 0.000000000 -0.127062867 Nuclear contribution : -0.000000009 0.000000000 0.973089124 ----------------------------------------- Total Dipole Moment : -0.000000005 0.000000000 0.846026256 ----------------------------------------- Magnitude (a.u.) : 0.846026256 Magnitude (Debye) : 2.150427846 -------------------- Rotational spectrum -------------------- Rotational constants in cm-1: 27.556575 14.280893 9.406222 Rotational constants in MHz : 826125.349454 428130.402685 281991.434304 Dipole components along the rotational axes: x,y,z [a.u.] : 0.000000 0.846026 -0.000000 x,y,z [Debye]: 0.000000 2.150428 -0.000000 Dipole moment calculation done in 0.0 sec Maximum memory used throughout the entire PROP-calculation: 3.9 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_dlpnoccsdt.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.; Hansen, A.; Liakos, D.G. Efficient and accurate approximations to the local coupled cluster singles doubles method using a truncated pair natural orbital basis J. Chem. Phys. 2009 131 , 064103 doi.org/10.1063/1.3173827 2. Neese, F.; Wennmohs, F.; Hansen, A. Efficient and accurate local approximations to coupled-electron pair approaches: An attempt to revive the pair natural orbital method J. Chem. Phys. 2009 130 , 114108 doi.org/10.1063/1.3086717 3. Riplinger, C.; Neese, F. An efficient and near linear scaling pair natural orbital based local coupled cluster method J. Chem. Phys. 2013 138(3), Art. No. 034106 doi.org/10.1063/1.4773581 4. Riplinger, C.; Sandhoefer, B.; Hansen, A.; Neese, F. Natural triple excitations in local coupled cluster calculations with pair natural orbitals J. Chem. Phys. 2013 139(13), Art. No. 134101 doi.org/10.1063/1.4821834 5. Riplinger, C.; Pinski, P.; Becker, U.; Valeev, E.F.; Neese, F. Sparse maps-A systematic infrastructure for reduced-scaling electronic structure methods. II. Linear scaling domain based pair natural orbital coupled cluster theory J. Chem. Phys. 2016 144 , doi.org/10.1063/1.4939030 6. Bistoni, G.; Riplinger, C.; Minenkov, Y.; Cavallo, L.; Auer, A.A.; Neese, F. Treating Subvalence Correlation Effects in Domain Based Pair Natural Orbital Coupled Cluster Calculations: An Out-of-the-Box Approach J. Theo. Comp. Chem. 2017 13 , 3220-3227 doi.org/10.1021/acs.jctc.7b00352 7. Stoychev, G.L.; Auer, A.A.; Neese, F. Automatic Generation of Auxiliary Basis Sets J. Theo. Comp. Chem. 2017 13 , 554-562 doi.org/10.1021/acs.jctc.6b01041 8. 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. Neese, F. The ORCA program system WIRES Comput. Molec. Sci. 2012 2(1), 73-78 doi.org/10.1002/wcms.81 2. 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 3. 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 4. 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 ... 4.424 sec (= 0.074 min) Startup calculation ... 0.098 sec (= 0.002 min) 2.2 % SCF iterations ... 0.445 sec (= 0.007 min) 10.1 % Property integrals ... 0.042 sec (= 0.001 min) 1.0 % Property calculations ... 0.040 sec (= 0.001 min) 0.9 % MDCI module ... 3.798 sec (= 0.063 min) 85.9 % ****ORCA TERMINATED NORMALLY**** TOTAL RUN TIME: 0 days 0 hours 0 minutes 4 seconds 533 msec