***************** * O R C A * ***************** #, ### #### ##### ###### ########, ,,################,,,,, ,,#################################,, ,,##########################################,, ,#########################################, ''#####, ,#############################################,, '####, ,##################################################,,,,####, ,###########'''' ''''############################### ,#####'' ,,,,##########,,,, '''####''' '#### ,##' ,,,,###########################,,, '## ' ,,###'''' '''############,,, ,,##'' '''############,,,, ,,,,,,###'' ,#'' '''#######################''' ' ''''####'''' ,#######, #######, ,#######, ## ,#' '#, ## ## ,#' '#, #''# ###### ,####, ## ## ## ,#' ## #' '# # #' '# ## ## ####### ## ,######, #####, # # '#, ,#' ## ## '#, ,#' ,# #, ## #, ,# '#######' ## ## '#######' #' '# #####' # '####' ####################################################### # -***- # # Department of theory and spectroscopy # # Directorship and core code : Frank Neese # # Max Planck Institute fuer Kohlenforschung # # Kaiser Wilhelm Platz 1 # # D-45470 Muelheim/Ruhr # # Germany # # # # All rights reserved # # -***- # ####################################################### Program Version 5.0.3 - RELEASE - With contributions from (in alphabetic order): 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 : Parallelization Giovanni Bistoni : ED, misc. LED, open-shell LED, HFLD Martin Brehm : Molecular dynamics Dmytro Bykov : SCF Hessian Vijay G. Chilkuri : MRCI spin determinant printing, contributions to CSF-ICE Dipayan Datta : RHF DLPNO-CCSD density Achintya Kumar Dutta : EOM-CC, STEOM-CC Dmitry Ganyushin : Spin-Orbit,Spin-Spin,Magnetic field MRCI Miquel Garcia : C-PCM and meta-GGA Hessian, CC/C-PCM, Gaussian charge scheme Yang Guo : DLPNO-NEVPT2, F12-NEVPT2, CIM, IAO-localization Andreas Hansen : Spin unrestricted coupled pair/coupled cluster methods Benjamin Helmich-Paris : MC-RPA, TRAH-SCF, COSX integrals Lee Huntington : MR-EOM, pCC Robert Izsak : Overlap fitted RIJCOSX, COSX-SCS-MP3, EOM Marcus Kettner : VPT2 Christian Kollmar : KDIIS, OOCD, Brueckner-CCSD(T), CCSD density, CASPT2, CASPT2-K Simone Kossmann : Meta GGA functionals, TD-DFT gradient, OOMP2, MP2 Hessian Martin Krupicka : Initial AUTO-CI Lucas Lang : DCDCAS Marvin Lechner : AUTO-CI (C++ implementation), FIC-MRCC Dagmar Lenk : GEPOL surface, SMD Dimitrios Liakos : Extrapolation schemes; Compound Job, initial MDCI parallelization Dimitrios Manganas : Further ROCIS development; embedding schemes Dimitrios Pantazis : SARC Basis sets Anastasios Papadopoulos: AUTO-CI, single reference methods and gradients Taras Petrenko : DFT Hessian,TD-DFT gradient, ASA, ECA, R-Raman, ABS, FL, XAS/XES, NRVS Peter Pinski : DLPNO-MP2, DLPNO-MP2 Gradient Christoph Reimann : Effective Core Potentials Marius Retegan : Local ZFS, SOC Christoph Riplinger : Optimizer, TS searches, QM/MM, DLPNO-CCSD(T), (RO)-DLPNO pert. Triples Tobias Risthaus : Range-separated hybrids, TD-DFT gradient, RPA, STAB Michael Roemelt : Original ROCIS implementation Masaaki Saitow : Open-shell DLPNO-CCSD energy and density Barbara Sandhoefer : DKH picture change effects Avijit Sen : IP-ROCIS Kantharuban Sivalingam : CASSCF convergence, NEVPT2, FIC-MRCI Bernardo de Souza : ESD, SOC TD-DFT Georgi Stoychev : AutoAux, RI-MP2 NMR, DLPNO-MP2 response Willem Van den Heuvel : Paramagnetic NMR Boris Wezisla : Elementary symmetry handling Frank Wennmohs : Technical directorship We gratefully acknowledge several colleagues who have allowed us to interface, adapt or use parts of their codes: Stefan Grimme, W. Hujo, H. Kruse, P. Pracht, : VdW corrections, initial TS optimization, C. Bannwarth, S. Ehlert DFT functionals, gCP, sTDA/sTD-DF 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) Jiri Pittner, Ondrej Demel : Mk-CCSD Frank Weinhold : gennbo (NPA and NBO analysis) Christopher J. Cramer and Donald G. Truhlar : smd solvation model Lars Goerigk : TD-DFT with DH, B97 family of functionals V. Asgeirsson, H. Jonsson : NEB implementation FAccTs GmbH : IRC, NEB, NEB-TS, DLPNO-Multilevel, CI-OPT MM, QMMM, 2- and 3-layer-ONIOM, Crystal-QMMM, LR-CPCM, SF, NACMEs, symmetry and pop. for TD-DFT, nearIR, NL-DFT gradient (VV10), updates on ESD, ML-optimized integration grids 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: 5.1.0 For citations please refer to: https://tddft.org/programs/libxc/ 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 0.3.15 USE64BITINT DYNAMIC_ARCH NO_AFFINITY Haswell SINGLE_THREADED Core in use : Haswell Copyright (c) 2011-2014, The OpenBLAS Project *************************************** The coordinates will be read from file: fch3f.xyz *************************************** Your calculation utilizes a Nudged-Elastic-Band implementation by V.Asgeirsson, C. Riplinger & H. Jonsson Please cite in your paper: V. Asgeirsson et al., in prep. (2019) ================================================================================ ----- 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 F. Weigend, Phys. Chem. Chem. Phys. 8, 1057 (2006). ================================================================================ WARNINGS Please study these warnings very carefully! ================================================================================ WARNING: Geometry Optimization ===> : Switching off AutoStart For restart on a previous wavefunction, please use MOREAD INFO : the flag for use of the SHARK integral package has been found! ================================================================================ INPUT FILE ================================================================================ NAME = sn2.inp | 1> ! B3LYP neb-ts | 2> * xyzfile -1 1 fch3f.xyz | 3> | 4> %neb | 5> product "prodotti.xyz" | 6> nimages 16 | 7> end | 8> | 9> | 10> ****END OF INPUT**** ================================================================================ -------------------------------------------------------------------------------- Nudged Elastic Band Calculation -------------------------------------------------------------------------------- Number of images (incl. end points) .... 18 Number of intermediate images .... 16 Number of optimized images .... 16 Optimization of end points before NEB .... NO Use existing gbw files for MO input .... NO Number of atoms .... 6 Number of (active) degrees of freedom .... 18 Constrained atoms .... None ----------------------------------------- REACTANT (ANGSTROEM) ----------------------------------------- C 0.001999 0.001370 0.619993 F -0.010548 -0.005389 2.050530 H 1.020937 -0.110658 0.233182 H -0.403372 0.937641 0.220825 H -0.598678 -0.816099 0.206519 F -0.010363 -0.006890 -1.788215 ----------------------------------------- PRODUCT (ANGSTROEM) ----------------------------------------- C -0.000109 0.002676 0.560704 F -0.000076 -0.013265 2.969918 H 1.012202 -0.106915 0.964870 H -0.410333 0.943137 0.945164 H -0.604696 -0.813160 0.971847 F 0.002987 -0.012497 -0.869669 ---------------------- NEB settings ---------------------- Method type .... climbing image Threshold for climbing image .... 2.00e-02 Eh/Bohr Free endpoints .... off Tangent type .... improved Number of intermediate images .... 16 Number of images free to move .... 16 Spring type for image distribution .... distance between adjacent images Spring constant .... energy weighted (0.0100 -to- 0.1000) Eh/Bohr^2 Spring force perp. to the path .... none Generation of initial path .... image dependent pair potential Initial path via TS guess .... off Minimization of RMSD: Rotation .... always Minimization of RMSD: Translation type .... centroid Center fixed to origin .... true Remove external force .... true Reparametrization of the path .... off Convergence thresholds: Convergence monitored for .... all images Scaling factor .... 10.00 Convergence parameters for regular images: Max(|Fp|) .... 2.00e-02 Eh/Bohr RMS(Fp) .... 1.00e-02 Eh/Bohr Convergence parameters for climbing image: Max(|F|) .... 2.00e-03 Eh/Bohr RMS(F) .... 1.00e-03 Eh/Bohr Optimization method: Method .... L-BFGS Max. iterations .... 500 Step size .... 1.00 Maximum allowed step size .... 0.10 Bohr LBFGS parameters: Memory .... 20 Initial step size .... 0.0010 Estimate curvature .... YES Reset on maxmove .... YES Reparam. on reset .... NO Generation of the initial path: Minimize RMSD between reactant and product configurations .... done RMSD before minimization .... 0.8139 Bohr RMSD after minimization .... 0.3651 Bohr Performing linear interpolation .... done Interpolation using .... IDPP (Image Dependent Pair Potential) IDPP-Settings: Remove global transl. and rot. ... true Convergence tolerance .... 0.0100 1/Ang.^3 Max. numer of iterations .... 7000 Spring constant .... 1.0000 1/Ang.^4 Time step .... 0.0100 fs Max. movement per iteration .... 0.0500 Ang. Full print .... false idpp initial path generation successfully converged in 93 iterations Displacement along initial path: 1.6057 Bohr Writing initial trajectory to file .... sn2_initial_path_trj.xyz ---------------------- NEB OPTIMIZATION ---------------------- Following output files will be written: Energy profile during opt. written to .... sn2.interp Optimization log-file .... sn2.NEB.log Current trajectory will be written to .... sn2_MEP_trj.xyz and to allxyz file .... sn2_MEP.allxyz and individual images to xyz file .... sn2_im{NIm}.xyz Trajectory history will be written to .... sn2_MEP_ALL_trj.xyz Converged CI will be written to .... sn2_NEB-CI_converged.xyz Converged TS will be written to .... sn2_NEB-TS_converged.xyz Single point energy and gradient calculation of reactant and product configurations (have to be performed only once) Properties of fixed NEB end points: Reactant: E .... -239.266548 Eh RMS(F) .... 0.000048 Eh/Bohr MAX(|F|) .... 0.000098 Eh/Bohr Product: E .... -239.266548 Eh RMS(F) .... 0.000029 Eh/Bohr MAX(|F|) .... 0.000068 Eh/Bohr Starting iterations: Optim. Iteration HEI E(HEI)-E(0) max(|Fp|) RMS(Fp) dS Switch-on CI threshold 0.020000 LBFGS 0 8 0.020799 0.019027 0.005554 1.6057 Image 8 will be converted to a climbing image in the next iteration (max(|Fp|) < 0.0200) Optim. Iteration CI E(CI)-E(0) max(|Fp|) RMS(Fp) dS max(|FCI|) RMS(FCI) Convergence thresholds 0.020000 0.010000 0.002000 0.001000 LBFGS 1 8 0.018576 0.011214 0.004287 1.7413 0.012202 0.004625 LBFGS 2 8 0.017444 0.010189 0.002653 1.8319 0.009970 0.003673 LBFGS 3 8 0.017997 0.029713 0.005465 1.8544 0.029691 0.009707 LBFGS 4 8 0.017213 0.003496 0.001067 1.8349 0.001347 0.000636 .--------------------. ----------------------| CI-NEB convergence |------------------------- Item value Tolerance Converged --------------------------------------------------------------------- RMS(Fp) 0.0010667130 0.0100000000 YES MAX(|Fp|) 0.0034958466 0.0200000000 YES RMS(FCI) 0.0006361726 0.0010000000 YES MAX(|FCI|) 0.0013465772 0.0020000000 YES --------------------------------------------------------------------- The elastic band and climbing image have converged successfully to a MEP in 4 iterations! *********************H U R R A Y********************* *** THE NEB OPTIMIZATION HAS CONVERGED *** ***************************************************** --------------------------------------------------------------- PATH SUMMARY --------------------------------------------------------------- All forces in Eh/Bohr. Image Dist.(Ang.) E(Eh) dE(kcal/mol) max(|Fp|) RMS(Fp) 0 0.000 -239.26655 0.00 0.00010 0.00005 1 0.093 -239.26556 0.62 0.00208 0.00093 2 0.156 -239.26360 1.85 0.00286 0.00135 3 0.209 -239.26114 3.40 0.00348 0.00155 4 0.260 -239.25820 5.24 0.00253 0.00140 5 0.311 -239.25514 7.16 0.00234 0.00118 6 0.362 -239.25244 8.85 0.00206 0.00092 7 0.415 -239.25037 10.15 0.00156 0.00066 8 0.479 -239.24933 10.80 0.00122 0.00053 <= CI 9 0.515 -239.24952 10.69 0.00125 0.00052 10 0.560 -239.25052 10.06 0.00162 0.00063 11 0.609 -239.25247 8.83 0.00199 0.00086 12 0.659 -239.25518 7.14 0.00231 0.00112 13 0.711 -239.25824 5.21 0.00256 0.00138 14 0.762 -239.26117 3.38 0.00350 0.00155 15 0.815 -239.26362 1.84 0.00286 0.00135 16 0.878 -239.26558 0.61 0.00208 0.00094 17 0.971 -239.26655 -0.00 0.00007 0.00003 Straight line distance between images along the path: D( 0- 1) = 0.0928 Ang. D( 1- 2) = 0.0635 Ang. D( 2- 3) = 0.0527 Ang. D( 3- 4) = 0.0513 Ang. D( 4- 5) = 0.0511 Ang. D( 5- 6) = 0.0505 Ang. D( 6- 7) = 0.0531 Ang. D( 7- 8) = 0.0636 Ang. D( 8- 9) = 0.0362 Ang. D( 9-10) = 0.0451 Ang. D(10-11) = 0.0490 Ang. D(11-12) = 0.0504 Ang. D(12-13) = 0.0512 Ang. D(13-14) = 0.0513 Ang. D(14-15) = 0.0527 Ang. D(15-16) = 0.0636 Ang. D(16-17) = 0.0928 Ang. --------------------------------------------------------------- INFORMATION ABOUT SADDLE POINT --------------------------------------------------------------- Climbing image .... 8 Energy .... -239.24933482 Eh Max. abs. force .... 1.3466e-03 Eh/Bohr ----------------------------------------- SADDLE POINT (ANGSTROEM) ----------------------------------------- C 0.000466 0.001232 0.005724 F -0.005354 -0.008590 1.808273 H 1.079456 -0.116439 0.005302 H -0.432439 0.997747 -0.003486 H -0.643343 -0.870804 -0.003501 F 0.001215 -0.003147 -1.812313 ----------------------------------------- FORCES (Eh/Bohr) ----------------------------------------- C 0.000146 0.001213 0.001347 F 0.000054 0.000307 -0.001330 H 0.000005 -0.000282 -0.000501 H 0.000081 -0.000696 0.000041 H -0.000451 -0.000731 -0.000208 F 0.000283 0.000143 0.000639 ----------------------------------------- UNIT TANGENT ----------------------------------------- C 0.000695 0.002940 -0.891849 F -0.001499 -0.003077 0.294201 H 0.000421 -0.000754 0.099850 H 0.000222 0.000839 0.097595 H -0.000005 -0.002093 0.104071 F 0.000166 0.002145 0.296132 => Unit tangent is an approximation to the TS mode at the saddle point Next a TS optimization is performed on the CI from the NEB run. ************************************************************* * TS OPTIMIZATION * ************************************************************* Following output files will be written: Converged TS will be written to .... sn2_NEB-TS_converged.xyz .... sn2.xyz Current trajectory will be written to .... sn2_trj.xyz Initial Hessian will be stored in .... sn2.appr.hess Geometry optimization settings: Update method Update .... Bofill Choice of coordinates CoordSys .... Z-matrix Internals Initial Hessian InHess .... Read 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 new redundant internal coordinates Making redundant internal coordinates ... (new redundants) done Following TS mode number ... 0 TS-active-atoms for coordinate setup... 0 Evaluating the initial hessian ... (Reading Exact Hessian)... InHessName: sn2.appr.hess The file is opened as a .hess file done done Diagonalizing the Hessian .... done Dimension of the hessian .... 14 Lowest eigenvalues of the non projected Hessian: -0.028240994 -0.000000000 -0.000000000 0.111058048 0.225545663 done Evaluating the coordinates ... done Calculating the B-matrix .... done Calculating the G-matrix .... done Diagonalizing the G-matrix .... done The first mode is .... 2 The number of degrees of freedom .... 12 ----------------------------------------------------------------- Redundant Internal Coordinates ----------------------------------------------------------------- Definition Initial Value d2E/dq (diagonal element) ----------------------------------------------------------------- 1. B(F 1,C 0) 1.8026 0.083635 2. B(H 2,C 0) 1.0854 0.366253 3. B(H 3,C 0) 1.0865 0.364727 4. B(H 4,C 0) 1.0840 0.368149 5. B(F 5,C 0) 1.8180 0.081760 6. A(F 1,C 0,H 3) 90.6983 0.202541 7. A(H 2,C 0,H 3) 119.7035 0.194885 8. A(F 1,C 0,H 4) 90.1266 0.201167 9. A(H 2,C 0,H 4) 120.2125 0.195042 10. A(H 3,C 0,H 4) 120.0740 0.194942 11. A(H 2,C 0,F 5) 89.9393 0.200570 12. A(H 3,C 0,F 5) 89.6503 0.200993 13. A(H 4,C 0,F 5) 89.4153 0.199732 14. A(F 1,C 0,H 2) 90.1723 0.202136 ----------------------------------------------------------------- Number of atoms .... 6 Number of degrees of freedom .... 14 ************************************************************* * GEOMETRY OPTIMIZATION CYCLE 1 * ************************************************************* ------------------------------------------------------------------------------ ORCA GTO INTEGRAL CALCULATION -- 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 ------------------------------------------------------------------------------ Reading SHARK input file sn2.SHARKINP.tmp ... ok ---------------------- SHARK INTEGRAL PACKAGE ---------------------- Number of atoms ... 6 Number of basis functions ... 57 Number of shells ... 27 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 Coulomb Range Separation ... NOT USED Exchange Range Separation ... NOT USED Finite Nucleus Model ... NOT USED Auxiliary Coulomb fitting basis ... AVAILABLE # of basis functions in Aux-J ... 180 # of shells in Aux-J ... 60 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 Integral threshold ... 2.500000e-11 Primitive cut-off ... 2.500000e-12 Primitive pair pre-selection threshold ... 2.500000e-12 Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 27 Organizing shell pair data ... done ( 0.0 sec) Shell pair information Total number of shell pairs ... 378 Shell pairs after pre-screening ... 368 Total number of primitive shell pairs ... 1374 Primitive shell pairs kept ... 1124 la=0 lb=0: 115 shell pairs la=1 lb=0: 133 shell pairs la=1 lb=1: 44 shell pairs la=2 lb=0: 43 shell pairs la=2 lb=1: 27 shell pairs la=2 lb=2: 6 shell pairs Calculating one electron integrals ... done ( 0.0 sec) Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 66.568631235138 Eh SHARK setup successfully completed in 0.1 seconds Maximum memory used throughout the entire GTOINT-calculation: 9.1 MB ------------------------------------------------------------------------------- ORCA SCF ------------------------------------------------------------------------------- ------------ 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 Density functional embedding theory .... OFF NL short-range parameter .... 4.800000 RI-approximation to the Coulomb term is turned on Number of AuxJ basis functions .... 180 RIJ-COSX (HFX calculated with COS-X)).... on General Settings: Integral files IntName .... sn2 Hartree-Fock type HFTyp .... RHF Total Charge Charge .... -1 Multiplicity Mult .... 1 Number of Electrons NEL .... 28 Basis Dimension Dim .... 57 Nuclear Repulsion ENuc .... 66.5686312351 Eh Convergence Acceleration: 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 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 .... 16 Max. Number of Macro iterations .... Maxiter - #DIIS iter Number of Davidson start vectors .... 2 Converg. threshold I (grad. norm) .... 1.000e-05 Converg. threshold II (energy diff.) .... 1.000e-08 Grad. Scal. Fac. for Micro threshold .... 0.100 Minimum threshold for Micro iter. .... 0.010 NR start threshold (gradient norm) .... 0.001 Initial trust radius .... 0.400 Minimum AH scaling param. (alpha) .... 1.000 Maximum AH scaling param. (alpha) .... 1000.000 Orbital update algorithm .... Taylor White noise on init. David. guess .... on Maximum white noise .... 0.010 Quad. conv. algorithm .... NR SOSCF CNVSOSCF .... on Start iteration SOSCFMaxIt .... 150 Startup grad/error SOSCFStart .... 0.003300 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 Fernandez-Rico CNVRico .... off 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 Diagonalization of the overlap matrix: Smallest eigenvalue ... 1.196e-02 Time for diagonalization ... 0.001 sec Threshold for overlap eigenvalues ... 1.000e-08 Number of eigenvalues below threshold ... 0 Time for construction of square roots ... 0.000 sec Total time needed ... 0.001 sec --------------------- INITIAL GUESS: MOREAD --------------------- Guess MOs are being read from file: sn2.gbw Input Geometry matches current geometry (good) Input basis set matches current basis set (good) MOs were renormalized MOs were reorthogonalized (Cholesky) ------------------ INITIAL GUESS DONE ( 0.0 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... Becke Basis function cutoff BFCut ... 1.0000e-11 Integration weight cutoff WCut ... 1.0000e-14 Angular grids for H and He will be reduced by one unit Partially contracted basis set ... off Rotationally invariant grid construction ... off Total number of grid points ... 28188 Total number of batches ... 444 Average number of points per batch ... 63 Average number of grid points per atom ... 4698 Time for grid setup = 0.159 sec -------------------- 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... Becke Basis function cutoff BFCut ... 1.0000e-11 Integration weight cutoff WCut ... 1.0000e-14 Angular grids for H and He will be reduced by one unit Partially contracted basis set ... on Rotationally invariant grid construction ... off Total number of grid points ... 3614 Total number of batches ... 60 Average number of points per batch ... 60 Average number of grid points per atom ... 602 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... Becke Basis function cutoff BFCut ... 1.0000e-11 Integration weight cutoff WCut ... 1.0000e-14 Angular grids for H and He will be reduced by one unit Partially contracted basis set ... on Rotationally invariant grid construction ... off Total number of grid points ... 7991 Total number of batches ... 127 Average number of points per batch ... 62 Average number of grid points per atom ... 1332 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... Becke Basis function cutoff BFCut ... 1.0000e-11 Integration weight cutoff WCut ... 1.0000e-14 Angular grids for H and He will be reduced by one unit Partially contracted basis set ... on Rotationally invariant grid construction ... off Total number of grid points ... 17682 Total number of batches ... 281 Average number of points per batch ... 62 Average number of grid points per atom ... 2947 UseSFitting ... on Time for X-Grid setup = 0.145 sec -------------- SCF ITERATIONS -------------- ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp *** Starting incremental Fock matrix formation *** *** Initiating the SOSCF procedure *** *** Re-Reading the Fockian *** *** Removing any level shift *** ITER Energy Delta-E Grad Rot Max-DP RMS-DP 0 -239.24941868 -239.2494186810 0.000012 0.000012 0.000028 0.000001 *** Restarting incremental Fock matrix formation *** 1 -239.24941868 0.0000000001 0.000013 0.000036 0.000045 0.000002 2 -239.24941868 0.0000000025 0.000026 0.000028 0.000030 0.000001 **** Energy Check signals convergence **** ***Rediagonalizing the Fockian in SOSCF/NRSCF*** ***************************************************** * SUCCESS * * SCF CONVERGED AFTER 3 CYCLES * ***************************************************** Old exchange energy = -5.319750876 Eh New exchange energy = -5.319667018 Eh Exchange energy change after final integration = 0.000083858 Eh Total energy after final integration = -239.249334824 Eh Final COS-X integration done in = 0.581 sec ---------------- TOTAL SCF ENERGY ---------------- Total Energy : -239.24933482 Eh -6510.30538 eV Components: Nuclear Repulsion : 66.56863124 Eh 1811.42455 eV Electronic Energy : -305.81796606 Eh -8321.72993 eV One Electron Energy: -473.10042860 Eh -12873.71715 eV Two Electron Energy: 167.28246254 Eh 4551.98722 eV Max COSX asymmetry : 0.00000115 Eh 0.00003 eV Virial components: Potential Energy : -477.11889514 Eh -12983.06518 eV Kinetic Energy : 237.86956032 Eh 6472.75980 eV Virial Ratio : 2.00580055 DFT components: N(Alpha) : 14.000005776145 electrons N(Beta) : 14.000005776145 electrons N(Total) : 28.000011552290 electrons E(X) : -21.179038272998 Eh E(C) : -1.160156200114 Eh E(XC) : -22.339194473112 Eh DFET-embed. en. : 0.000000000000 Eh --------------- SCF CONVERGENCE --------------- Last Energy change ... -3.0199e-09 Tolerance : 1.0000e-08 Last MAX-Density change ... 3.1086e-15 Tolerance : 1.0000e-07 Last RMS-Density change ... 8.9071e-17 Tolerance : 5.0000e-09 Last Orbital Gradient ... 6.1995e-07 Tolerance : 1.0000e-05 Last Orbital Rotation ... 1.4681e-06 Tolerance : 1.0000e-05 **** THE GBW FILE WAS UPDATED (sn2.gbw) **** **** DENSITY sn2.scfp WAS UPDATED **** **** ENERGY FILE WAS UPDATED (sn2.en.tmp) **** **** THE GBW FILE WAS UPDATED (sn2.gbw) **** **** DENSITY sn2.scfp WAS UPDATED **** ---------------- ORBITAL ENERGIES ---------------- NO OCC E(Eh) E(eV) 0 2.0000 -24.298374 -661.1924 1 2.0000 -24.293237 -661.0526 2 2.0000 -10.023594 -272.7559 3 2.0000 -0.756267 -20.5791 4 2.0000 -0.747672 -20.3452 5 2.0000 -0.437750 -11.9118 6 2.0000 -0.217326 -5.9137 7 2.0000 -0.216389 -5.8882 8 2.0000 -0.123684 -3.3656 9 2.0000 -0.043164 -1.1746 10 2.0000 -0.043156 -1.1743 11 2.0000 -0.025423 -0.6918 12 2.0000 -0.025355 -0.6899 13 2.0000 -0.015806 -0.4301 14 0.0000 0.270683 7.3656 15 0.0000 0.309826 8.4308 16 0.0000 0.329847 8.9756 17 0.0000 0.330530 8.9942 18 0.0000 0.676179 18.3998 19 0.0000 0.677245 18.4288 20 0.0000 0.787673 21.4337 21 0.0000 0.794311 21.6143 22 0.0000 0.877326 23.8733 23 0.0000 0.878762 23.9123 24 0.0000 0.974671 26.5222 25 0.0000 1.264444 34.4073 26 0.0000 1.265802 34.4442 27 0.0000 1.457151 39.6511 28 0.0000 1.462130 39.7866 29 0.0000 1.506184 40.9854 30 0.0000 1.506856 41.0036 31 0.0000 1.659495 45.1572 32 0.0000 1.661321 45.2068 33 0.0000 1.685261 45.8583 34 0.0000 1.743722 47.4491 35 0.0000 1.907868 51.9157 36 0.0000 1.908114 51.9224 37 0.0000 1.984426 53.9990 38 0.0000 2.246537 61.1314 39 0.0000 2.398590 65.2690 40 0.0000 2.427070 66.0439 41 0.0000 2.430557 66.1388 42 0.0000 2.438128 66.3448 43 0.0000 2.441823 66.4454 44 0.0000 3.019188 82.1563 45 0.0000 3.107221 84.5518 46 0.0000 3.109334 84.6093 47 0.0000 3.441775 93.6555 48 0.0000 3.441861 93.6578 49 0.0000 3.447130 93.8012 50 0.0000 3.447155 93.8019 51 0.0000 3.453168 93.9655 52 0.0000 3.453324 93.9697 53 0.0000 3.485178 94.8365 54 0.0000 3.485308 94.8401 55 0.0000 3.503943 95.3471 56 0.0000 3.741507 101.8116 ------- TIMINGS ------- Total SCF time: 0 days 0 hours 0 min 2 sec Total time .... 2.517 sec Sum of individual times .... 2.454 sec ( 97.5%) Fock matrix formation .... 2.147 sec ( 85.3%) Split-RI-J .... 0.182 sec ( 8.5% of F) Chain of spheres X .... 1.607 sec ( 74.9% of F) XC integration .... 0.364 sec ( 17.0% of F) Basis function eval. .... 0.141 sec ( 38.6% of XC) Density eval. .... 0.081 sec ( 22.2% of XC) XC-Functional eval. .... 0.054 sec ( 14.9% of XC) XC-Potential eval. .... 0.061 sec ( 16.7% of XC) Diagonalization .... 0.001 sec ( 0.0%) Density matrix formation .... 0.000 sec ( 0.0%) Population analysis .... 0.000 sec ( 0.0%) Initial guess .... 0.001 sec ( 0.1%) Orbital Transformation .... 0.000 sec ( 0.0%) Orbital Orthonormalization .... 0.001 sec ( 0.0%) DIIS solution .... 0.000 sec ( 0.0%) SOSCF solution .... 0.001 sec ( 0.0%) Grid generation .... 0.304 sec ( 12.1%) Maximum memory used throughout the entire SCF-calculation: 46.7 MB ------------------------- -------------------- FINAL SINGLE POINT ENERGY -239.249334823765 ------------------------- -------------------- ------------------------------------------------------------------------------ ORCA SCF GRADIENT CALCULATION ------------------------------------------------------------------------------ ... reading COSX grid (gridx3) Gradient of the Kohn-Sham DFT energy: Kohn-Sham wavefunction type ... RKS Hartree-Fock exchange scaling ... 0.200 Number of operators ... 1 Number of atoms ... 6 Basis set dimensions ... 57 Integral neglect threshold ... 2.5e-11 Integral primitive cutoff ... 2.5e-12 SHARK Integral package ... ON Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) RI-J gradient (SHARK) ... done ( 0.1 sec) COSX-gradient ... done ( 0.8 sec) Exchange-correlation gradient ... done ------------------ CARTESIAN GRADIENT ------------------ 1 C : -0.000146274 -0.001214091 -0.001347951 2 F : -0.000054242 -0.000306670 0.001329806 3 H : -0.000006027 0.000282237 0.000501642 4 H : -0.000080803 0.000695028 -0.000040417 5 H : 0.000451819 0.000732368 0.000208800 6 F : -0.000282886 -0.000143242 -0.000639675 Difference to translation invariance: : -0.0001184124 0.0000456292 0.0000122040 Difference to rotation invariance: : 0.0000259886 -0.0000069914 0.0000114011 Norm of the cartesian gradient ... 0.0027007689 RMS gradient ... 0.0006365773 MAX gradient ... 0.0013479514 ------- TIMINGS ------- Total SCF gradient time ... 1.615 sec One electron gradient .... 0.011 sec ( 0.7%) RI-J Coulomb gradient .... 0.102 sec ( 6.3%) COSX gradient .... 0.848 sec ( 52.5%) XC gradient .... 0.518 sec ( 32.1%) Maximum memory used throughout the entire SCFGRAD-calculation: 36.1 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 .... (new redundants).... done Validating the new internal coordinates .... (new 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 .... 6 Number of internal coordinates .... 14 Current Energy .... -239.249334824 Eh Current gradient norm .... 0.002700769 Eh/bohr Maximum allowed component of the step .... 0.300 Current trust radius .... 0.100 Evaluating the initial hessian .... (read) (Reading Exact Hessian)... InHessName: sn2.appr.hess The file is opened as a .hess file done done Diagonalizing the Hessian .... done Dimension of the hessian .... 14 Lowest eigenvalues of the non projected Hessian: -0.028240994 -0.000000000 -0.000000000 0.111058048 0.225545663 done Projecting the Hessian .... done Diagonalizing the Hessian .... done Dimension of the hessian .... 14 Lowest eigenvalues of the Hessian: -0.028240994 0.111058048 0.225545663 0.264798421 0.265017571 Hessian has 1 negative eigenvalues Taking P-RFO step Searching for lambda that maximizes along the lowest mode TS mode is mode number 0 with eigenvalue -0.02824099 and components: 1. -0.57999204 2. 0.00004986 3. 0.00459692 4. 0.00169957 5. 0.58164504 6. 0.23136318 7. -0.00468241 8. 0.23437873 9. -0.00214250 10. -0.00719318 11. -0.23253062 12. -0.23178595 13. -0.23409680 14. 0.23267393 Lambda that maximizes along the TS mode: 0.00001795 Searching for lambda that minimizes along all other modes In cycle 1: lambdaN = -0.00002695 step = 0.00002695 In cycle 2: lambdaN = -0.00002695 step = 0.00000000 Lambda that minimizes along all other modes: -0.00002695 The final length of the internal step .... 0.0287 Converting the step to cartesian space: Initial RMS(Int)= 0.0076779856 Transforming coordinates: Iter 0: RMS(Cart)= 0.0049258340 RMS(Int)= 0.0076767122 Iter 1: RMS(Cart)= 0.0000153171 RMS(Int)= 0.0000165455 Iter 2: RMS(Cart)= 0.0000000630 RMS(Int)= 0.0000000675 done Storing new coordinates .... done .--------------------. ----------------------|Geometry convergence|------------------------- Item value Tolerance Converged --------------------------------------------------------------------- RMS gradient 0.0006147316 0.0001000000 NO MAX gradient 0.0013295669 0.0003000000 NO RMS step 0.0076779856 0.0020000000 NO MAX step 0.0238861496 0.0040000000 NO ........................................................ Max(Bonds) 0.0126 Max(Angles) 0.46 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 comp.(TS mode) ---------------------------------------------------------------------------- 1. B(F 1,C 0) 1.8026 0.001330 0.0032 1.8058 0.58 2. B(H 2,C 0) 1.0854 -0.000016 0.0000 1.0854 3. B(H 3,C 0) 1.0865 0.000655 -0.0010 1.0855 4. B(H 4,C 0) 1.0840 -0.000865 0.0012 1.0852 5. B(F 5,C 0) 1.8180 0.000642 -0.0126 1.8054 0.58 6. A(F 1,C 0,H 3) 90.70 0.000382 -0.45 90.25 7. A(H 2,C 0,H 3) 119.70 -0.000331 0.07 119.78 8. A(F 1,C 0,H 4) 90.13 -0.000820 -0.19 89.93 9. A(H 2,C 0,H 4) 120.21 0.000227 -0.04 120.17 10. A(H 3,C 0,H 4) 120.07 0.000118 -0.01 120.06 11. A(H 2,C 0,F 5) 89.94 0.000789 0.20 90.14 12. A(H 3,C 0,F 5) 89.65 0.000303 0.30 89.95 13. A(H 4,C 0,F 5) 89.42 -0.000411 0.46 89.87 14. A(F 1,C 0,H 2) 90.17 -0.000236 -0.32 89.86 ---------------------------------------------------------------------------- ************************************************************* * GEOMETRY OPTIMIZATION CYCLE 2 * ************************************************************* --------------------------------- CARTESIAN COORDINATES (ANGSTROEM) --------------------------------- C -0.000156 0.000552 0.000055 F -0.004094 -0.005530 1.805838 H 1.078769 -0.117836 0.004749 H -0.433184 0.995945 -0.002288 H -0.644587 -0.872583 -0.003009 F 0.003251 -0.000548 -1.805344 ---------------------------- CARTESIAN COORDINATES (A.U.) ---------------------------- NO LB ZA FRAG MASS X Y Z 0 C 6.0000 0 12.011 -0.000295 0.001044 0.000103 1 F 9.0000 0 18.998 -0.007736 -0.010451 3.412539 2 H 1.0000 0 1.008 2.038577 -0.222678 0.008974 3 H 1.0000 0 1.008 -0.818599 1.882064 -0.004324 4 H 1.0000 0 1.008 -1.218092 -1.648943 -0.005686 5 F 9.0000 0 18.998 0.006144 -0.001036 -3.411607 -------------------------------- INTERNAL COORDINATES (ANGSTROEM) -------------------------------- C 0 0 0 0.000000000000 0.00000000 0.00000000 F 1 0 0 1.805797994225 0.00000000 0.00000000 H 1 2 0 1.085410610928 89.85536013 0.00000000 H 1 2 3 1.085507083905 90.25077337 240.22757392 H 1 2 3 1.085202993115 89.93227138 120.16852054 F 1 2 3 1.805402587794 179.77144880 87.95792604 --------------------------- INTERNAL COORDINATES (A.U.) --------------------------- C 0 0 0 0.000000000000 0.00000000 0.00000000 F 1 0 0 3.412463662270 0.00000000 0.00000000 H 1 2 0 2.051128797507 89.85536013 0.00000000 H 1 2 3 2.051311105012 90.25077337 240.22757392 H 1 2 3 2.050736456700 89.93227138 120.16852054 F 1 2 3 3.411716452403 179.77144880 87.95792604 ------------------------------------------------------------------------------ ___ / \ - 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 ------------------------------------------------------------------------------ Reading SHARK input file sn2.SHARKINP.tmp ... ok ---------------------- SHARK INTEGRAL PACKAGE ---------------------- Number of atoms ... 6 Number of basis functions ... 57 Number of shells ... 27 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 Coulomb Range Separation ... NOT USED Exchange Range Separation ... NOT USED Finite Nucleus Model ... NOT USED Auxiliary Coulomb fitting basis ... AVAILABLE # of basis functions in Aux-J ... 180 # of shells in Aux-J ... 60 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 Integral threshold ... 2.500000e-11 Primitive cut-off ... 2.500000e-12 Primitive pair pre-selection threshold ... 2.500000e-12 Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 27 Organizing shell pair data ... done ( 0.0 sec) Shell pair information Total number of shell pairs ... 378 Shell pairs after pre-screening ... 368 Total number of primitive shell pairs ... 1374 Primitive shell pairs kept ... 1125 la=0 lb=0: 115 shell pairs la=1 lb=0: 133 shell pairs la=1 lb=1: 44 shell pairs la=2 lb=0: 43 shell pairs la=2 lb=1: 27 shell pairs la=2 lb=2: 6 shell pairs Calculating one electron integrals ... done ( 0.0 sec) Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 66.706242563551 Eh SHARK setup successfully completed in 0.1 seconds Maximum memory used throughout the entire GTOINT-calculation: 9.1 MB Diagonalization of the overlap matrix: Smallest eigenvalue ... 1.192e-02 Time for diagonalization ... 0.001 sec Threshold for overlap eigenvalues ... 1.000e-08 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... Becke Basis function cutoff BFCut ... 1.0000e-11 Integration weight cutoff WCut ... 1.0000e-14 Angular grids for H and He will be reduced by one unit Partially contracted basis set ... off Rotationally invariant grid construction ... off Total number of grid points ... 28189 Total number of batches ... 445 Average number of points per batch ... 63 Average number of grid points per atom ... 4698 Time for grid setup = 0.187 sec -------------------- 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... Becke Basis function cutoff BFCut ... 1.0000e-11 Integration weight cutoff WCut ... 1.0000e-14 Angular grids for H and He will be reduced by one unit Partially contracted basis set ... on Rotationally invariant grid construction ... off Total number of grid points ... 3614 Total number of batches ... 60 Average number of points per batch ... 60 Average number of grid points per atom ... 602 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... Becke Basis function cutoff BFCut ... 1.0000e-11 Integration weight cutoff WCut ... 1.0000e-14 Angular grids for H and He will be reduced by one unit Partially contracted basis set ... on Rotationally invariant grid construction ... off Total number of grid points ... 7991 Total number of batches ... 128 Average number of points per batch ... 62 Average number of grid points per atom ... 1332 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... Becke Basis function cutoff BFCut ... 1.0000e-11 Integration weight cutoff WCut ... 1.0000e-14 Angular grids for H and He will be reduced by one unit Partially contracted basis set ... on Rotationally invariant grid construction ... off Total number of grid points ... 17682 Total number of batches ... 281 Average number of points per batch ... 62 Average number of grid points per atom ... 2947 UseSFitting ... on Time for X-Grid setup = 0.140 sec -------------- SCF ITERATIONS -------------- ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp *** Starting incremental Fock matrix formation *** *** Initiating the SOSCF procedure *** *** Re-Reading the Fockian *** *** Removing any level shift *** ITER Energy Delta-E Grad Rot Max-DP RMS-DP 0 -239.24938616 -239.2493861624 0.001809 0.001809 0.002932 0.000210 *** Restarting incremental Fock matrix formation *** 1 -239.24942032 -0.0000341619 0.000592 0.001568 0.001848 0.000145 2 -239.24942223 -0.0000019023 0.000759 0.000837 0.001005 0.000076 3 -239.24942491 -0.0000026825 0.000156 0.000231 0.000619 0.000044 4 -239.24942529 -0.0000003809 0.000050 0.000099 0.000114 0.000007 5 -239.24942528 0.0000000100 0.000070 0.000064 0.000072 0.000005 6 -239.24942531 -0.0000000268 0.000003 0.000007 0.000014 0.000001 ***Gradient check signals convergence*** ***Rediagonalizing the Fockian in SOSCF/NRSCF*** ***************************************************** * SUCCESS * * SCF CONVERGED AFTER 7 CYCLES * ***************************************************** Old exchange energy = -5.320083220 Eh New exchange energy = -5.320001062 Eh Exchange energy change after final integration = 0.000082157 Eh Total energy after final integration = -239.249343150 Eh Final COS-X integration done in = 0.610 sec Total Energy : -239.24934315 Eh -6510.30560 eV Last Energy change ... -1.1599e-10 Tolerance : 1.0000e-08 Last MAX-Density change ... 3.1086e-15 Tolerance : 1.0000e-07 **** THE GBW FILE WAS UPDATED (sn2.gbw) **** **** DENSITY sn2.scfp WAS UPDATED **** **** ENERGY FILE WAS UPDATED (sn2.en.tmp) **** **** THE GBW FILE WAS UPDATED (sn2.gbw) **** **** DENSITY sn2.scfp WAS UPDATED **** Total SCF time: 0 days 0 hours 0 min 3 sec Maximum memory used throughout the entire SCF-calculation: 46.7 MB ------------------------- -------------------- FINAL SINGLE POINT ENERGY -239.249343149638 ------------------------- -------------------- ------------------------------------------------------------------------------ ORCA SCF GRADIENT CALCULATION ------------------------------------------------------------------------------ ... reading COSX grid (gridx3) Gradient of the Kohn-Sham DFT energy: Kohn-Sham wavefunction type ... RKS Hartree-Fock exchange scaling ... 0.200 Number of operators ... 1 Number of atoms ... 6 Basis set dimensions ... 57 Integral neglect threshold ... 2.5e-11 Integral primitive cutoff ... 2.5e-12 SHARK Integral package ... ON Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) RI-J gradient (SHARK) ... done ( 0.1 sec) COSX-gradient ... done ( 0.7 sec) Exchange-correlation gradient ... done ------------------ CARTESIAN GRADIENT ------------------ 1 C : -0.000159781 -0.000195777 0.000018270 2 F : 0.000014277 -0.000135066 0.000212382 3 H : -0.000080750 0.000251769 0.000164387 4 H : 0.000204819 -0.000034597 -0.000219461 5 H : 0.000063394 0.000190413 -0.000060622 6 F : -0.000153439 -0.000028220 -0.000113076 Difference to translation invariance: : -0.0001114796 0.0000485208 0.0000018800 Difference to rotation invariance: : 0.0000115709 -0.0000160579 0.0000117868 Norm of the cartesian gradient ... 0.0006301302 RMS gradient ... 0.0001485231 MAX gradient ... 0.0002517688 ------- TIMINGS ------- Total SCF gradient time ... 1.481 sec One electron gradient .... 0.011 sec ( 0.7%) RI-J Coulomb gradient .... 0.102 sec ( 6.9%) COSX gradient .... 0.709 sec ( 47.8%) XC gradient .... 0.530 sec ( 35.8%) Maximum memory used throughout the entire SCFGRAD-calculation: 36.1 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 .... (new redundants).... done Validating the new internal coordinates .... (new 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 .... 6 Number of internal coordinates .... 14 Current Energy .... -239.249343150 Eh Current gradient norm .... 0.000630130 Eh/bohr Maximum allowed component of the step .... 0.300 Current trust radius .... 0.100 Updating the Hessian (Bofill) .... Diagonalizing the Hessian .... done Dimension of the hessian .... 14 Lowest eigenvalues of the Hessian: -0.024309470 0.104881386 0.225842193 0.261185401 0.264883593 Hessian has 1 negative eigenvalues Taking P-RFO step Searching for lambda that maximizes along the lowest mode TS mode is mode number 0 with eigenvalue -0.02430947 and components: 1. -0.54423921 2. -0.00698366 3. -0.00644950 4. -0.01300974 5. 0.60096860 6. 0.26978754 7. -0.03118173 8. 0.21735942 9. 0.01793410 10. 0.00403157 11. -0.20547840 12. -0.24137651 13. -0.26470601 14. 0.22469294 Lambda that maximizes along the TS mode: 0.00000015 Searching for lambda that minimizes along all other modes In cycle 1: lambdaN = -0.00000254 step = 0.00000254 In cycle 2: lambdaN = -0.00000254 step = 0.00000000 Lambda that minimizes along all other modes: -0.00000254 The final length of the internal step .... 0.0044 Converting the step to cartesian space: Initial RMS(Int)= 0.0011822272 Transforming coordinates: Iter 0: RMS(Cart)= 0.0012671671 RMS(Int)= 0.0011820171 Iter 1: RMS(Cart)= 0.0000006924 RMS(Int)= 0.0000007152 Iter 2: RMS(Cart)= 0.0000000005 RMS(Int)= 0.0000000004 done Storing new coordinates .... done The predicted energy change is .... -0.000001199 Previously predicted energy change .... -0.000004495 Actually observed energy change .... -0.000008326 Ratio of predicted to observed change .... 1.852292133 New trust radius .... 0.100000000 .--------------------. ----------------------|Geometry convergence|------------------------- Item value Tolerance Converged --------------------------------------------------------------------- Energy change -0.0000083259 0.0000050000 NO RMS gradient 0.0002035121 0.0001000000 NO MAX gradient 0.0003670348 0.0003000000 NO RMS step 0.0011822272 0.0020000000 YES MAX step 0.0034456330 0.0040000000 YES ........................................................ Max(Bonds) 0.0018 Max(Angles) 0.09 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 comp.(TS mode) ---------------------------------------------------------------------------- 1. B(F 1,C 0) 1.8058 0.000212 -0.0018 1.8040 0.54 2. B(H 2,C 0) 1.0854 -0.000088 0.0001 1.0855 3. B(H 3,C 0) 1.0855 -0.000128 0.0002 1.0857 4. B(H 4,C 0) 1.0852 -0.000195 0.0003 1.0855 5. B(F 5,C 0) 1.8054 0.000113 0.0001 1.8055 0.60 6. A(F 1,C 0,H 3) 90.25 0.000367 -0.04 90.21 0.27 7. A(H 2,C 0,H 3) 119.77 -0.000289 0.05 119.83 8. A(F 1,C 0,H 4) 89.93 -0.000170 0.07 90.00 9. A(H 2,C 0,H 4) 120.17 0.000190 -0.04 120.13 10. A(H 3,C 0,H 4) 120.06 0.000099 -0.02 120.04 11. A(H 2,C 0,F 5) 90.14 0.000260 -0.09 90.05 12. A(H 3,C 0,F 5) 89.95 -0.000086 -0.02 89.93 13. A(H 4,C 0,F 5) 89.87 -0.000293 0.03 89.90 0.26 14. A(F 1,C 0,H 2) 89.86 -0.000075 0.05 89.91 ---------------------------------------------------------------------------- ************************************************************* * GEOMETRY OPTIMIZATION CYCLE 3 * ************************************************************* --------------------------------- CARTESIAN COORDINATES (ANGSTROEM) --------------------------------- C -0.000331 0.000246 0.000624 F -0.003759 -0.004295 1.804590 H 1.078656 -0.118731 0.004150 H -0.433863 0.995613 -0.001642 H -0.644845 -0.873180 -0.002885 F 0.004141 0.000347 -1.804838 ---------------------------- CARTESIAN COORDINATES (A.U.) ---------------------------- NO LB ZA FRAG MASS X Y Z 0 C 6.0000 0 12.011 -0.000626 0.000465 0.001180 1 F 9.0000 0 18.998 -0.007103 -0.008117 3.410181 2 H 1.0000 0 1.008 2.038365 -0.224370 0.007842 3 H 1.0000 0 1.008 -0.819881 1.881437 -0.003103 4 H 1.0000 0 1.008 -1.218581 -1.650071 -0.005451 5 F 9.0000 0 18.998 0.007826 0.000656 -3.410649 -------------------------------- INTERNAL COORDINATES (ANGSTROEM) -------------------------------- C 0 0 0 0.000000000000 0.00000000 0.00000000 F 1 0 0 1.803974643755 0.00000000 0.00000000 H 1 2 0 1.085533267299 89.90630481 0.00000000 H 1 2 3 1.085684587039 90.20837610 240.17202022 H 1 2 3 1.085487171587 90.00454230 120.13211274 F 1 2 3 1.805467876593 179.85514784 70.50135992 --------------------------- INTERNAL COORDINATES (A.U.) --------------------------- C 0 0 0 0.000000000000 0.00000000 0.00000000 F 1 0 0 3.409018029235 0.00000000 0.00000000 H 1 2 0 2.051360584457 89.90630481 0.00000000 H 1 2 3 2.051646537322 90.20837610 240.17202022 H 1 2 3 2.051273476184 90.00454230 120.13211274 F 1 2 3 3.411839830353 179.85514784 70.50135992 ------------------------------------------------------------------------------ ___ / \ - 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 ------------------------------------------------------------------------------ Reading SHARK input file sn2.SHARKINP.tmp ... ok ---------------------- SHARK INTEGRAL PACKAGE ---------------------- Number of atoms ... 6 Number of basis functions ... 57 Number of shells ... 27 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 Coulomb Range Separation ... NOT USED Exchange Range Separation ... NOT USED Finite Nucleus Model ... NOT USED Auxiliary Coulomb fitting basis ... AVAILABLE # of basis functions in Aux-J ... 180 # of shells in Aux-J ... 60 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 Integral threshold ... 2.500000e-11 Primitive cut-off ... 2.500000e-12 Primitive pair pre-selection threshold ... 2.500000e-12 Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 27 Organizing shell pair data ... done ( 0.0 sec) Shell pair information Total number of shell pairs ... 378 Shell pairs after pre-screening ... 368 Total number of primitive shell pairs ... 1374 Primitive shell pairs kept ... 1125 la=0 lb=0: 115 shell pairs la=1 lb=0: 133 shell pairs la=1 lb=1: 44 shell pairs la=2 lb=0: 43 shell pairs la=2 lb=1: 27 shell pairs la=2 lb=2: 6 shell pairs Calculating one electron integrals ... done ( 0.0 sec) Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 66.729905623574 Eh SHARK setup successfully completed in 0.1 seconds Maximum memory used throughout the entire GTOINT-calculation: 9.1 MB Diagonalization of the overlap matrix: Smallest eigenvalue ... 1.192e-02 Time for diagonalization ... 0.001 sec Threshold for overlap eigenvalues ... 1.000e-08 Number of eigenvalues below threshold ... 0 Time for construction of square roots ... 0.000 sec Total time needed ... 0.002 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... Becke Basis function cutoff BFCut ... 1.0000e-11 Integration weight cutoff WCut ... 1.0000e-14 Angular grids for H and He will be reduced by one unit Partially contracted basis set ... off Rotationally invariant grid construction ... off Total number of grid points ... 28189 Total number of batches ... 445 Average number of points per batch ... 63 Average number of grid points per atom ... 4698 Time for grid setup = 0.169 sec -------------------- 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... Becke Basis function cutoff BFCut ... 1.0000e-11 Integration weight cutoff WCut ... 1.0000e-14 Angular grids for H and He will be reduced by one unit Partially contracted basis set ... on Rotationally invariant grid construction ... off Total number of grid points ... 3614 Total number of batches ... 60 Average number of points per batch ... 60 Average number of grid points per atom ... 602 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... Becke Basis function cutoff BFCut ... 1.0000e-11 Integration weight cutoff WCut ... 1.0000e-14 Angular grids for H and He will be reduced by one unit Partially contracted basis set ... on Rotationally invariant grid construction ... off Total number of grid points ... 7991 Total number of batches ... 128 Average number of points per batch ... 62 Average number of grid points per atom ... 1332 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... Becke Basis function cutoff BFCut ... 1.0000e-11 Integration weight cutoff WCut ... 1.0000e-14 Angular grids for H and He will be reduced by one unit Partially contracted basis set ... on Rotationally invariant grid construction ... off Total number of grid points ... 17682 Total number of batches ... 281 Average number of points per batch ... 62 Average number of grid points per atom ... 2947 UseSFitting ... on Time for X-Grid setup = 0.140 sec -------------- SCF ITERATIONS -------------- ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp *** Starting incremental Fock matrix formation *** *** Initiating the SOSCF procedure *** *** Re-Reading the Fockian *** *** Removing any level shift *** ITER Energy Delta-E Grad Rot Max-DP RMS-DP 0 -239.24942589 -239.2494258881 0.000206 0.000206 0.000552 0.000037 *** Restarting incremental Fock matrix formation *** 1 -239.24942674 -0.0000008554 0.000069 0.000195 0.000358 0.000028 2 -239.24942684 -0.0000000952 0.000078 0.000105 0.000193 0.000014 3 -239.24942688 -0.0000000367 0.000035 0.000063 0.000127 0.000009 4 -239.24942690 -0.0000000208 0.000009 0.000021 0.000032 0.000001 5 -239.24942689 0.0000000013 0.000015 0.000014 0.000020 0.000001 ***Gradient check signals convergence*** ***Rediagonalizing the Fockian in SOSCF/NRSCF*** ***************************************************** * SUCCESS * * SCF CONVERGED AFTER 6 CYCLES * ***************************************************** Old exchange energy = -5.320101144 Eh New exchange energy = -5.320019482 Eh Exchange energy change after final integration = 0.000081662 Eh Total energy after final integration = -239.249345234 Eh Final COS-X integration done in = 0.564 sec Total Energy : -239.24934523 Eh -6510.30566 eV Last Energy change ... -1.6267e-09 Tolerance : 1.0000e-08 Last MAX-Density change ... 2.2204e-15 Tolerance : 1.0000e-07 **** THE GBW FILE WAS UPDATED (sn2.gbw) **** **** DENSITY sn2.scfp WAS UPDATED **** **** ENERGY FILE WAS UPDATED (sn2.en.tmp) **** **** THE GBW FILE WAS UPDATED (sn2.gbw) **** **** DENSITY sn2.scfp WAS UPDATED **** Total SCF time: 0 days 0 hours 0 min 3 sec Maximum memory used throughout the entire SCF-calculation: 46.7 MB ------------------------- -------------------- FINAL SINGLE POINT ENERGY -239.249345234166 ------------------------- -------------------- ------------------------------------------------------------------------------ ORCA SCF GRADIENT CALCULATION ------------------------------------------------------------------------------ ... reading COSX grid (gridx3) Gradient of the Kohn-Sham DFT energy: Kohn-Sham wavefunction type ... RKS Hartree-Fock exchange scaling ... 0.200 Number of operators ... 1 Number of atoms ... 6 Basis set dimensions ... 57 Integral neglect threshold ... 2.5e-11 Integral primitive cutoff ... 2.5e-12 SHARK Integral package ... ON Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) RI-J gradient (SHARK) ... done ( 0.1 sec) COSX-gradient ... done ( 0.7 sec) Exchange-correlation gradient ... done ------------------ CARTESIAN GRADIENT ------------------ 1 C : -0.000129823 -0.000218393 -0.000134281 2 F : 0.000024632 -0.000062146 0.000068331 3 H : -0.000013701 0.000190042 0.000155390 4 H : 0.000117770 0.000057058 -0.000119705 5 H : -0.000013508 0.000068164 -0.000005943 6 F : -0.000094490 0.000014975 0.000039682 Difference to translation invariance: : -0.0001091208 0.0000497008 0.0000034746 Difference to rotation invariance: : 0.0000114539 -0.0000163178 0.0000116080 Norm of the cartesian gradient ... 0.0004463349 RMS gradient ... 0.0001052021 MAX gradient ... 0.0002183929 ------- TIMINGS ------- Total SCF gradient time ... 1.462 sec One electron gradient .... 0.011 sec ( 0.8%) RI-J Coulomb gradient .... 0.101 sec ( 6.9%) COSX gradient .... 0.687 sec ( 47.0%) XC gradient .... 0.534 sec ( 36.5%) Maximum memory used throughout the entire SCFGRAD-calculation: 36.1 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 .... (new redundants).... done Validating the new internal coordinates .... (new 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 .... 6 Number of internal coordinates .... 14 Current Energy .... -239.249345234 Eh Current gradient norm .... 0.000446335 Eh/bohr Maximum allowed component of the step .... 0.300 Current trust radius .... 0.100 (DQ * DQ)^2 = 0.00000000083544 Bofill update is skipped Updating the Hessian (Bofill) .... (DQ * DQ)^2 = 0.00000000038287 Bofill update is skipped Diagonalizing the Hessian .... done Dimension of the hessian .... 14 Lowest eigenvalues of the Hessian: -0.024309470 0.104881386 0.225842193 0.261185401 0.264883593 Hessian has 1 negative eigenvalues Taking P-RFO step Searching for lambda that maximizes along the lowest mode TS mode is mode number 0 with eigenvalue -0.02430947 and components: 1. -0.54423921 2. -0.00698366 3. -0.00644950 4. -0.01300974 5. 0.60096860 6. 0.26978754 7. -0.03118173 8. 0.21735942 9. 0.01793410 10. 0.00403157 11. -0.20547840 12. -0.24137651 13. -0.26470601 14. 0.22469294 Lambda that maximizes along the TS mode: 0.00000009 Searching for lambda that minimizes along all other modes In cycle 1: lambdaN = -0.00000069 step = 0.00000069 In cycle 2: lambdaN = -0.00000069 step = 0.00000000 Lambda that minimizes along all other modes: -0.00000069 The final length of the internal step .... 0.0025 Converting the step to cartesian space: Initial RMS(Int)= 0.0006650123 Transforming coordinates: Iter 0: RMS(Cart)= 0.0006615933 RMS(Int)= 0.0006650042 Iter 1: RMS(Cart)= 0.0000002793 RMS(Int)= 0.0000003315 Iter 2: RMS(Cart)= 0.0000000002 RMS(Int)= 0.0000000002 done Storing new coordinates .... done The predicted energy change is .... -0.000000301 Previously predicted energy change .... -0.000001199 Actually observed energy change .... -0.000002085 Ratio of predicted to observed change .... 1.738096984 New trust radius .... 0.100000000 .--------------------. ----------------------|Geometry convergence|------------------------- Item value Tolerance Converged --------------------------------------------------------------------- Energy change -0.0000020845 0.0000050000 YES RMS gradient 0.0001153165 0.0001000000 NO MAX gradient 0.0002223353 0.0003000000 YES RMS step 0.0006650123 0.0020000000 YES MAX step 0.0012746887 0.0040000000 YES ........................................................ Max(Bonds) 0.0007 Max(Angles) 0.07 Max(Dihed) 0.00 Max(Improp) 0.00 --------------------------------------------------------------------- The step convergence is overachieved with reasonable convergence on the gradient Convergence will therefore be signaled now ***********************HURRAY******************** *** THE OPTIMIZATION HAS CONVERGED *** ************************************************* --------------------------------------------------------------------------- Redundant Internal Coordinates --- Optimized Parameters --- (Angstroem and degrees) Definition OldVal dE/dq Step FinalVal comp.(TS mode) ---------------------------------------------------------------------------- 1. B(F 1,C 0) 1.8040 0.000068 0.0003 1.8043 0.54 2. B(H 2,C 0) 1.0855 -0.000015 0.0000 1.0856 3. B(H 3,C 0) 1.0857 -0.000009 0.0000 1.0857 4. B(H 4,C 0) 1.0855 -0.000051 0.0001 1.0856 5. B(F 5,C 0) 1.8055 -0.000039 -0.0007 1.8048 0.60 6. A(F 1,C 0,H 3) 90.21 0.000175 -0.07 90.14 0.27 7. A(H 2,C 0,H 3) 119.83 -0.000222 0.05 119.88 8. A(F 1,C 0,H 4) 90.00 -0.000075 -0.01 90.00 9. A(H 2,C 0,H 4) 120.13 0.000146 -0.03 120.10 10. A(H 3,C 0,H 4) 120.04 0.000077 -0.02 120.02 11. A(H 2,C 0,F 5) 90.05 0.000187 -0.02 90.03 12. A(H 3,C 0,F 5) 89.93 -0.000073 0.04 89.98 13. A(H 4,C 0,F 5) 89.90 -0.000086 0.05 89.95 0.26 14. A(F 1,C 0,H 2) 89.91 -0.000128 0.00 89.91 ---------------------------------------------------------------------------- ******************************************************* *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** *** (AFTER 3 CYCLES) *** ******************************************************* ------------------------------------------------------------------------------ ORCA GTO INTEGRAL CALCULATION -- 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 ------------------------------------------------------------------------------ Reading SHARK input file sn2.SHARKINP.tmp ... ok ---------------------- SHARK INTEGRAL PACKAGE ---------------------- Number of atoms ... 6 Number of basis functions ... 57 Number of shells ... 27 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 Coulomb Range Separation ... NOT USED Exchange Range Separation ... NOT USED Finite Nucleus Model ... NOT USED Auxiliary Coulomb fitting basis ... AVAILABLE # of basis functions in Aux-J ... 180 # of shells in Aux-J ... 60 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 Integral threshold ... 2.500000e-11 Primitive cut-off ... 2.500000e-12 Primitive pair pre-selection threshold ... 2.500000e-12 Calculating pre-screening integrals ... done ( 0.0 sec) Dimension = 27 Organizing shell pair data ... done ( 0.0 sec) Shell pair information Total number of shell pairs ... 378 Shell pairs after pre-screening ... 368 Total number of primitive shell pairs ... 1374 Primitive shell pairs kept ... 1125 la=0 lb=0: 115 shell pairs la=1 lb=0: 133 shell pairs la=1 lb=1: 44 shell pairs la=2 lb=0: 43 shell pairs la=2 lb=1: 27 shell pairs la=2 lb=2: 6 shell pairs Calculating one electron integrals ... done ( 0.0 sec) Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 66.734212346799 Eh SHARK setup successfully completed in 0.1 seconds Maximum memory used throughout the entire GTOINT-calculation: 9.1 MB ------------------------------------------------------------------------------- ORCA SCF ------------------------------------------------------------------------------- ------------ 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 Density functional embedding theory .... OFF NL short-range parameter .... 4.800000 RI-approximation to the Coulomb term is turned on Number of AuxJ basis functions .... 180 RIJ-COSX (HFX calculated with COS-X)).... on General Settings: Integral files IntName .... sn2 Hartree-Fock type HFTyp .... RHF Total Charge Charge .... -1 Multiplicity Mult .... 1 Number of Electrons NEL .... 28 Basis Dimension Dim .... 57 Nuclear Repulsion ENuc .... 66.7342123468 Eh Convergence Acceleration: 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 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 .... 16 Max. Number of Macro iterations .... Maxiter - #DIIS iter Number of Davidson start vectors .... 2 Converg. threshold I (grad. norm) .... 1.000e-05 Converg. threshold II (energy diff.) .... 1.000e-08 Grad. Scal. Fac. for Micro threshold .... 0.100 Minimum threshold for Micro iter. .... 0.010 NR start threshold (gradient norm) .... 0.001 Initial trust radius .... 0.400 Minimum AH scaling param. (alpha) .... 1.000 Maximum AH scaling param. (alpha) .... 1000.000 Orbital update algorithm .... Taylor White noise on init. David. guess .... on Maximum white noise .... 0.010 Quad. conv. algorithm .... NR SOSCF CNVSOSCF .... on Start iteration SOSCFMaxIt .... 150 Startup grad/error SOSCFStart .... 0.003300 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 Fernandez-Rico CNVRico .... off 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 Diagonalization of the overlap matrix: Smallest eigenvalue ... 1.192e-02 Time for diagonalization ... 0.001 sec Threshold for overlap eigenvalues ... 1.000e-08 Number of eigenvalues below threshold ... 0 Time for construction of square roots ... 0.000 sec Total time needed ... 0.001 sec --------------------- INITIAL GUESS: MOREAD --------------------- Guess MOs are being read from file: sn2.gbw Input Geometry matches current geometry (good) Input basis set matches current basis set (good) MOs were renormalized MOs were reorthogonalized (Cholesky) ------------------ INITIAL GUESS DONE ( 0.0 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... Becke Basis function cutoff BFCut ... 1.0000e-11 Integration weight cutoff WCut ... 1.0000e-14 Angular grids for H and He will be reduced by one unit Partially contracted basis set ... off Rotationally invariant grid construction ... off Total number of grid points ... 28189 Total number of batches ... 445 Average number of points per batch ... 63 Average number of grid points per atom ... 4698 Time for grid setup = 0.162 sec -------------------- 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... Becke Basis function cutoff BFCut ... 1.0000e-11 Integration weight cutoff WCut ... 1.0000e-14 Angular grids for H and He will be reduced by one unit Partially contracted basis set ... on Rotationally invariant grid construction ... off Total number of grid points ... 3614 Total number of batches ... 60 Average number of points per batch ... 60 Average number of grid points per atom ... 602 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... Becke Basis function cutoff BFCut ... 1.0000e-11 Integration weight cutoff WCut ... 1.0000e-14 Angular grids for H and He will be reduced by one unit Partially contracted basis set ... on Rotationally invariant grid construction ... off Total number of grid points ... 7991 Total number of batches ... 128 Average number of points per batch ... 62 Average number of grid points per atom ... 1332 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... Becke Basis function cutoff BFCut ... 1.0000e-11 Integration weight cutoff WCut ... 1.0000e-14 Angular grids for H and He will be reduced by one unit Partially contracted basis set ... on Rotationally invariant grid construction ... off Total number of grid points ... 17683 Total number of batches ... 281 Average number of points per batch ... 62 Average number of grid points per atom ... 2947 UseSFitting ... on Time for X-Grid setup = 0.149 sec -------------- SCF ITERATIONS -------------- ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp *** Starting incremental Fock matrix formation *** *** Initiating the SOSCF procedure *** *** Re-Reading the Fockian *** *** Removing any level shift *** ITER Energy Delta-E Grad Rot Max-DP RMS-DP 0 -239.24942703 -239.2494270310 0.000131 0.000131 0.000375 0.000023 *** Restarting incremental Fock matrix formation *** 1 -239.24942729 -0.0000002613 0.000041 0.000113 0.000236 0.000015 2 -239.24942732 -0.0000000251 0.000057 0.000075 0.000123 0.000008 3 -239.24942733 -0.0000000104 0.000022 0.000031 0.000090 0.000005 4 -239.24942733 -0.0000000065 0.000003 0.000007 0.000007 0.000000 5 -239.24942733 0.0000000003 0.000005 0.000004 0.000004 0.000000 ***Gradient check signals convergence*** ***Rediagonalizing the Fockian in SOSCF/NRSCF*** ***************************************************** * SUCCESS * * SCF CONVERGED AFTER 6 CYCLES * ***************************************************** Old exchange energy = -5.320101884 Eh New exchange energy = -5.320020394 Eh Exchange energy change after final integration = 0.000081491 Eh Total energy after final integration = -239.249345843 Eh Final COS-X integration done in = 0.560 sec ---------------- TOTAL SCF ENERGY ---------------- Total Energy : -239.24934584 Eh -6510.30568 eV Components: Nuclear Repulsion : 66.73421235 Eh 1815.93024 eV Electronic Energy : -305.98355819 Eh -8326.23592 eV One Electron Energy: -473.43305202 Eh -12882.76829 eV Two Electron Energy: 167.44949383 Eh 4556.53238 eV Max COSX asymmetry : 0.00000114 Eh 0.00003 eV Virial components: Potential Energy : -477.12522510 Eh -12983.23743 eV Kinetic Energy : 237.87587926 Eh 6472.93175 eV Virial Ratio : 2.00577388 DFT components: N(Alpha) : 14.000006211106 electrons N(Beta) : 14.000006211106 electrons N(Total) : 28.000012422213 electrons E(X) : -21.180109832912 Eh E(C) : -1.160344995587 Eh E(XC) : -22.340454828500 Eh DFET-embed. en. : 0.000000000000 Eh --------------- SCF CONVERGENCE --------------- Last Energy change ... 3.9185e-10 Tolerance : 1.0000e-08 Last MAX-Density change ... 4.4409e-15 Tolerance : 1.0000e-07 Last RMS-Density change ... 1.0005e-16 Tolerance : 5.0000e-09 Last Orbital Gradient ... 1.6649e-07 Tolerance : 1.0000e-05 Last Orbital Rotation ... 3.0358e-07 Tolerance : 1.0000e-05 **** THE GBW FILE WAS UPDATED (sn2.gbw) **** **** DENSITY sn2.scfp WAS UPDATED **** **** ENERGY FILE WAS UPDATED (sn2.en.tmp) **** **** THE GBW FILE WAS UPDATED (sn2.gbw) **** **** DENSITY sn2.scfp WAS UPDATED **** ---------------- ORBITAL ENERGIES ---------------- NO OCC E(Eh) E(eV) 0 2.0000 -24.295854 -661.1238 1 2.0000 -24.295635 -661.1178 2 2.0000 -10.022913 -272.7373 3 2.0000 -0.755801 -20.5664 4 2.0000 -0.749175 -20.3861 5 2.0000 -0.436831 -11.8868 6 2.0000 -0.216580 -5.8934 7 2.0000 -0.216262 -5.8848 8 2.0000 -0.124345 -3.3836 9 2.0000 -0.043153 -1.1742 10 2.0000 -0.043130 -1.1736 11 2.0000 -0.025394 -0.6910 12 2.0000 -0.025376 -0.6905 13 2.0000 -0.015624 -0.4251 14 0.0000 0.271122 7.3776 15 0.0000 0.312812 8.5120 16 0.0000 0.330396 8.9905 17 0.0000 0.330509 8.9936 18 0.0000 0.677090 18.4246 19 0.0000 0.677776 18.4432 20 0.0000 0.786574 21.4038 21 0.0000 0.794564 21.6212 22 0.0000 0.878280 23.8992 23 0.0000 0.878523 23.9058 24 0.0000 0.975398 26.5419 25 0.0000 1.264179 34.4001 26 0.0000 1.264606 34.4117 27 0.0000 1.457818 39.6692 28 0.0000 1.462635 39.8003 29 0.0000 1.507143 41.0114 30 0.0000 1.507357 41.0173 31 0.0000 1.662602 45.2417 32 0.0000 1.663043 45.2537 33 0.0000 1.685755 45.8717 34 0.0000 1.746103 47.5139 35 0.0000 1.908677 51.9377 36 0.0000 1.909164 51.9510 37 0.0000 1.990000 54.1507 38 0.0000 2.246263 61.1239 39 0.0000 2.396772 65.2195 40 0.0000 2.432347 66.1875 41 0.0000 2.433706 66.2245 42 0.0000 2.434954 66.2585 43 0.0000 2.436131 66.2905 44 0.0000 3.017252 82.1036 45 0.0000 3.107594 84.5619 46 0.0000 3.108989 84.5999 47 0.0000 3.443009 93.6890 48 0.0000 3.443074 93.6908 49 0.0000 3.445537 93.7578 50 0.0000 3.445606 93.7597 51 0.0000 3.454217 93.9940 52 0.0000 3.454266 93.9953 53 0.0000 3.485427 94.8433 54 0.0000 3.485520 94.8458 55 0.0000 3.504085 95.3510 56 0.0000 3.751019 102.0704 ------- TIMINGS ------- Total SCF time: 0 days 0 hours 0 min 3 sec Total time .... 3.489 sec Sum of individual times .... 3.421 sec ( 98.0%) Fock matrix formation .... 3.105 sec ( 89.0%) Split-RI-J .... 0.221 sec ( 7.1% of F) Chain of spheres X .... 2.255 sec ( 72.6% of F) XC integration .... 0.633 sec ( 20.4% of F) Basis function eval. .... 0.250 sec ( 39.6% of XC) Density eval. .... 0.144 sec ( 22.7% of XC) XC-Functional eval. .... 0.096 sec ( 15.2% of XC) XC-Potential eval. .... 0.100 sec ( 15.8% of XC) Diagonalization .... 0.001 sec ( 0.0%) Density matrix formation .... 0.000 sec ( 0.0%) Population analysis .... 0.000 sec ( 0.0%) Initial guess .... 0.002 sec ( 0.0%) Orbital Transformation .... 0.000 sec ( 0.0%) Orbital Orthonormalization .... 0.001 sec ( 0.0%) DIIS solution .... 0.000 sec ( 0.0%) SOSCF solution .... 0.002 sec ( 0.1%) Grid generation .... 0.311 sec ( 8.9%) Maximum memory used throughout the entire SCF-calculation: 46.7 MB ------------------------- -------------------- FINAL SINGLE POINT ENERGY -239.249345842942 ------------------------- -------------------- *** OPTIMIZATION RUN DONE *** ***********************HURRAY************************ *** THE TS OPTIMIZATION HAS CONVERGED *** ***************************************************** --------------------------------------------------------------- PATH SUMMARY FOR NEB-TS --------------------------------------------------------------- All forces in Eh/Bohr. Global forces for TS. Image E(Eh) dE(kcal/mol) max(|Fp|) RMS(Fp) 0 -239.26655 0.00 0.00010 0.00005 1 -239.26556 0.62 0.00208 0.00093 2 -239.26360 1.85 0.00286 0.00135 3 -239.26114 3.40 0.00348 0.00155 4 -239.25820 5.24 0.00253 0.00140 5 -239.25514 7.16 0.00234 0.00118 6 -239.25244 8.85 0.00206 0.00092 7 -239.25037 10.15 0.00156 0.00066 8 -239.24933 10.80 0.00122 0.00053 <= CI TS -239.24935 10.79 0.00022 0.00011 <= TS 9 -239.24952 10.69 0.00125 0.00052 10 -239.25052 10.06 0.00162 0.00063 11 -239.25247 8.83 0.00199 0.00086 12 -239.25518 7.14 0.00231 0.00112 13 -239.25824 5.21 0.00256 0.00138 14 -239.26117 3.38 0.00350 0.00155 15 -239.26362 1.84 0.00286 0.00135 16 -239.26558 0.61 0.00208 0.00094 17 -239.26655 -0.00 0.00007 0.00003 ---------- STATISTICS ---------- For the individual parts of the NEB, NEB-CI or NEB-TS run: Number of iterations: NEB ... 5 55.6% TS optimization ... 4 44.4% Number of SCF / gradient calculations: NEB ... 98 96.1% TS optimization ... 4 3.9% ---------- TIMINGS ---------- For the individual parts of the NEB, NEB-CI or NEB-TS run: Total ... 878.473 sec NEB ... 859.703 sec 97.9% TS Optimization ... 18.770 sec 2.1% *************************************** * ORCA property calculations * *************************************** --------------------- Active property flags --------------------- (+) Dipole Moment ------------------------------------------------------------------------------ ORCA ELECTRIC PROPERTIES CALCULATION ------------------------------------------------------------------------------ Dipole Moment Calculation ... on Quadrupole Moment Calculation ... off Polarizability Calculation ... off GBWName ... sn2.gbw Electron density ... sn2.scfp The origin for moment calculation is the CENTER OF MASS = ( 0.000456, -0.001788 0.000044) ------------- DIPOLE MOMENT ------------- X Y Z Electronic contribution: 0.00110 -0.00434 0.00125 Nuclear contribution : -0.00163 0.00615 -0.00011 ----------------------------------------- Total Dipole Moment : -0.00053 0.00181 0.00114 ----------------------------------------- Magnitude (a.u.) : 0.00220 Magnitude (Debye) : 0.00559 -------------------- Rotational spectrum -------------------- Rotational constants in cm-1: 4.729967 0.134312 0.134308 Rotational constants in MHz : 141800.840197 4026.586667 4026.441729 Dipole components along the rotational axes: x,y,z [a.u.] : 0.001140 0.000915 0.001645 x,y,z [Debye]: 0.002897 0.002325 0.004182 Timings for individual modules: Sum of individual times ... 892.575 sec (= 14.876 min) GTO integral calculation ... 0.607 sec (= 0.010 min) 0.1 % SCF iterations ... 24.677 sec (= 0.411 min) 2.8 % SCF Gradient evaluation ... 7.483 sec (= 0.125 min) 0.8 % Geometry relaxation ... 0.105 sec (= 0.002 min) 0.0 % NEB Iterations ... 859.703 sec (= 14.328 min) 96.3 % ****ORCA TERMINATED NORMALLY**** TOTAL RUN TIME: 0 days 0 hours 14 minutes 38 seconds 712 msec