***************** * 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 5.0.1 - 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 Shared memory : Shared parallel matrices ================================================================================ ----- Orbital basis set information ----- Your calculation utilizes the basis: def2-SVP F. Weigend and R. Ahlrichs, Phys. Chem. Chem. Phys. 7, 3297 (2005). ----- AuxC basis set information ----- Your calculation utilizes the auxiliary basis: def2-SVP/C H-La, Hf-Rn : A. Hellweg, C. Hattig, S. Hofener and W. Klopper, Theor. Chem. Acc. 117, 587 (2007). Ce-Lu : J. Chmela and M. E. Harding, Mol. Phys. (2018). ----- AuxJK basis set information ----- Your calculation utilizes the auxiliary basis: def2/JK H-Ba, Hf-Rn: F. Weigend, J. Comput. Chem. 29, 167 (2008). ================================================================================ 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! INFO : the flag for use of the SHARK integral package has been found! ================================================================================ INPUT FILE ================================================================================ NAME = acrolein_DLPNO_STEOM_CCSD.inp | 1> ! STEOM-DLPNO-CCSD RIJK def2-SVP def2/JK def2-SVP/C tightSCF noautostart miniprint nopop | 2> %maxcore 4000 | 3> %pal nprocs 8 end | 4> %mdci | 5> nroots 5 | 6> end | 7> * xyz 0 1 | 8> O -1.21489126 -1.32839962 0.00000000 | 9> C -0.14662919 -0.74849643 0.00000000 | 10> C 0.00000000 0.71901245 0.00000000 | 11> H 0.81573680 -1.30939340 0.00000000 | 12> H -0.91954345 1.29882288 0.00000000 | 13> C 1.20813213 1.29246308 0.00000000 | 14> H 2.11426292 0.69032113 0.00000000 | 15> H 1.33965613 2.36957168 0.00000000 | 16> * | 17> | 18> ****END OF INPUT**** ================================================================================ **************************** * Single Point Calculation * **************************** --------------------------------- CARTESIAN COORDINATES (ANGSTROEM) --------------------------------- O -1.214891 -1.328400 0.000000 C -0.146629 -0.748496 0.000000 C 0.000000 0.719012 0.000000 H 0.815737 -1.309393 0.000000 H -0.919543 1.298823 0.000000 C 1.208132 1.292463 0.000000 H 2.114263 0.690321 0.000000 H 1.339656 2.369572 0.000000 ---------------------------- CARTESIAN COORDINATES (A.U.) ---------------------------- NO LB ZA FRAG MASS X Y Z 0 O 8.0000 0 15.999 -2.295812 -2.510311 0.000000 1 C 6.0000 0 12.011 -0.277089 -1.414453 0.000000 2 C 6.0000 0 12.011 0.000000 1.358737 0.000000 3 H 1.0000 0 1.008 1.541519 -2.474395 0.000000 4 H 1.0000 0 1.008 -1.737685 2.454420 0.000000 5 C 6.0000 0 12.011 2.283039 2.442401 0.000000 6 H 1.0000 0 1.008 3.995378 1.304518 0.000000 7 H 1.0000 0 1.008 2.531583 4.477842 0.000000 ************************************************************ * Program running with 8 parallel MPI-processes * * working on a common directory * ************************************************************ ------------------------------------------------------------------------------ ___ / \ - 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 acrolein_DLPNO_STEOM_CCSD.SHARKINP.tmp ... ok ---------------------- SHARK INTEGRAL PACKAGE ---------------------- Number of atoms ... 8 Number of basis functions ... 76 Number of shells ... 36 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 ... NOT available Auxiliary J/K fitting basis ... AVAILABLE # of basis functions in Aux-JK ... 374 # of shells in Aux-JK ... 124 Maximum angular momentum in Aux-JK ... 4 Auxiliary Correlation fitting basis ... AVAILABLE # of basis functions in Aux-C ... 248 # of shells in Aux-C ... 88 Maximum angular momentum in Aux-C ... 3 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 = 36 Organizing shell pair data ... done ( 0.0 sec) Shell pair information Total number of shell pairs ... 666 Shell pairs after pre-screening ... 653 Total number of primitive shell pairs ... 2410 Primitive shell pairs kept ... 1944 la=0 lb=0: 205 shell pairs la=1 lb=0: 236 shell pairs la=1 lb=1: 77 shell pairs la=2 lb=0: 78 shell pairs la=2 lb=1: 47 shell pairs la=2 lb=2: 10 shell pairs Calculating one electron integrals ... 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= 102.855628433179 Eh SHARK setup successfully completed in 0.1 seconds Maximum memory used throughout the entire GTOINT-calculation: 8.9 MB ************************************************************ * Program running with 8 parallel MPI-processes * * working on a common directory * ************************************************************ Diagonalization of the overlap matrix: Smallest eigenvalue ... 2.400e-03 Time for diagonalization ... 0.004 sec Threshold for overlap eigenvalues ... 1.000e-08 Number of eigenvalues below threshold ... 0 Time for construction of square roots ... 0.003 sec Total time needed ... 0.008 sec Time for model grid setup = 0.054 sec 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) Reading the grid ... done 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 -------------- SCF ITERATIONS -------------- ITER Energy Delta-E Max-DP RMS-DP [F,P] Damp 0 -190.4727692425 0.000000000000 0.05945717 0.00285948 0.2481712 0.7000 1 -190.3663328195 0.106436423001 0.06500579 0.00303845 0.2438467 0.7000 ***Turning on DIIS*** 2 -190.3777586308 -0.011425811302 0.04689759 0.00206237 0.1558886 0.7000 3 -190.7804043813 -0.402645750552 0.05760471 0.00356357 0.0651992 0.0000 4 -190.2975315925 0.482872788782 0.03299849 0.00129306 0.0447814 0.0000 5 -190.4343280683 -0.136796475765 0.01590065 0.00072283 0.0303207 0.0000 6 -190.5295782457 -0.095250177406 0.00593922 0.00032960 0.0107268 0.0000 7 -190.5889972622 -0.059419016452 0.00339670 0.00013876 0.0057268 0.0000 *** Initiating the SOSCF procedure *** *** Shutting down DIIS *** *** Re-Reading the Fockian *** *** Removing any level shift *** ITER Energy Delta-E Grad Rot Max-DP RMS-DP 8 -190.60684524 -0.0178479827 0.001332 0.001332 0.001835 0.000092 9 -190.61658493 -0.0097396809 0.000551 0.000882 0.001149 0.000042 10 -190.61658810 -0.0000031703 0.000206 0.000798 0.002151 0.000074 11 -190.61658962 -0.0000015270 0.000115 0.000061 0.000141 0.000009 12 -190.61658970 -0.0000000790 0.000029 0.000047 0.000048 0.000003 13 -190.61658971 -0.0000000084 0.000005 0.000006 0.000015 0.000001 14 -190.61658971 -0.0000000006 0.000003 0.000007 0.000005 0.000000 **** Energy Check signals convergence **** ***Rediagonalizing the Fockian in SOSCF/NRSCF*** ***************************************************** * SUCCESS * * SCF CONVERGED AFTER 15 CYCLES * ***************************************************** Total Energy : -190.61658971 Eh -5186.94111 eV Last Energy change ... -5.8492e-11 Tolerance : 1.0000e-08 Last MAX-Density change ... 1.4017e-06 Tolerance : 1.0000e-07 **** THE GBW FILE WAS UPDATED (acrolein_DLPNO_STEOM_CCSD.gbw) **** **** DENSITY acrolein_DLPNO_STEOM_CCSD.scfp WAS UPDATED **** **** ENERGY FILE WAS UPDATED (acrolein_DLPNO_STEOM_CCSD.en.tmp) **** **** THE GBW FILE WAS UPDATED (acrolein_DLPNO_STEOM_CCSD.gbw) **** **** DENSITY acrolein_DLPNO_STEOM_CCSD.scfp WAS UPDATED **** ---------------- ORBITAL ENERGIES ---------------- NO OCC E(Eh) E(eV) 0 2.0000 -20.553092 -559.2781 1 2.0000 -11.340582 -308.5929 2 2.0000 -11.277547 -306.8776 3 2.0000 -11.258597 -306.3620 4 2.0000 -1.372962 -37.3602 5 2.0000 -1.077424 -29.3182 6 2.0000 -0.877306 -23.8727 7 2.0000 -0.780403 -21.2359 8 2.0000 -0.671470 -18.2716 9 2.0000 -0.666348 -18.1323 10 2.0000 -0.606751 -16.5105 11 2.0000 -0.558453 -15.1963 12 2.0000 -0.541853 -14.7446 13 2.0000 -0.431679 -11.7466 14 2.0000 -0.400134 -10.8882 15 0.0000 0.082337 2.2405 16 0.0000 0.189142 5.1468 17 0.0000 0.199941 5.4407 18 0.0000 0.227013 6.1773 19 0.0000 0.249882 6.7996 20 0.0000 0.265751 7.2315 21 0.0000 0.369274 10.0485 22 0.0000 0.450806 12.2670 23 0.0000 0.487383 13.2624 24 0.0000 0.543376 14.7860 25 0.0000 0.600078 16.3290 26 0.0000 0.662175 18.0187 27 0.0000 0.665804 18.1174 28 0.0000 0.729063 19.8388 29 0.0000 0.738660 20.1000 30 0.0000 0.806246 21.9391 31 0.0000 0.825295 22.4574 32 0.0000 0.863099 23.4861 33 0.0000 0.867794 23.6139 34 0.0000 0.890651 24.2359 35 0.0000 0.936505 25.4836 36 0.0000 0.951709 25.8973 37 0.0000 1.051191 28.6044 38 0.0000 1.093259 29.7491 39 0.0000 1.231584 33.5131 40 0.0000 1.315505 35.7967 41 0.0000 1.360003 37.0076 42 0.0000 1.411305 38.4036 43 0.0000 1.419455 38.6253 44 0.0000 1.486886 40.4602 45 0.0000 1.491410 40.5833 46 0.0000 1.691225 46.0206 47 0.0000 1.700111 46.2624 48 0.0000 1.827357 49.7249 49 0.0000 1.870858 50.9086 50 0.0000 1.959453 53.3194 51 0.0000 1.967562 53.5401 52 0.0000 2.014450 54.8160 53 0.0000 2.056296 55.9547 54 0.0000 2.074716 56.4559 55 0.0000 2.102587 57.2143 56 0.0000 2.156051 58.6691 57 0.0000 2.315716 63.0138 58 0.0000 2.360571 64.2344 59 0.0000 2.368667 64.4547 60 0.0000 2.431849 66.1740 61 0.0000 2.587352 70.4054 62 0.0000 2.655983 72.2730 63 0.0000 2.778403 75.6042 64 0.0000 2.793123 76.0048 65 0.0000 2.821571 76.7789 66 0.0000 2.935355 79.8751 67 0.0000 3.077965 83.7557 68 0.0000 3.089480 84.0690 69 0.0000 3.112191 84.6870 70 0.0000 3.233795 87.9960 71 0.0000 3.328072 90.5614 72 0.0000 3.526698 95.9663 73 0.0000 3.675213 100.0076 74 0.0000 3.828029 104.1660 75 0.0000 4.024668 109.5168 Total SCF time: 0 days 0 hours 0 min 0 sec Maximum memory used throughout the entire SCF-calculation: 6.8 MB ************************************************************ * Program running with 8 parallel MPI-processes * * working on a common directory * ************************************************************ ------------------------------------------------------------------------------- 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 ... OFF Calculation of F12 correction ... OFF Frozen core treatment ... chemical core (8 el) Reference Wavefunction ... RHF Internal Orbitals: 4 ... 14 ( 11 MO's/ 22 electrons) Virtual Orbitals: 15 ... 75 ( 61 MO's ) Number of AO's ... 76 Number of electrons ... 30 Number of correlated electrons ... 22 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 ... 3.330e-07 Singles PNO occupation number cut-off ... 9.990e-09 PNO Mulliken prescreening cut-off ... 1.000e-03 Domain cut-off (Mulliken population) ... 1.000e-03 PNO Normalization ... 1 Maximum number of iterations ... 100 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 ... 4000 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-04 Eh Prescreening threshold for very weak pairs ... 1.000e-06 Eh Initializing the integral package ... done Localizing the valence orbitals ------------------------------------------------------------------------------ ORCA ORBITAL LOCALIZATION ------------------------------------------------------------------------------ Input orbitals are from ... acrolein_DLPNO_STEOM_CCSD.gbw Output orbitals are to ... acrolein_DLPNO_STEOM_CCSD.loc Max. number of iterations ... 128 Localizations seeded randomly ... off Convergence tolerance ... 1.000e-06 Using relative localization threshhold ... 1.000e-08 Treshold for strong local MOs ... 9.500e-01 Treshold for bond MOs ... 8.500e-01 Operator ... 0 Orbital range for localization ... 4 to 14 Localization criterion ... FOSTER-BOYS (AUGMENTED HESSIAN) Doing the dipole integrals ... o.k. Initial value of the localization sum : 72.593357 ITERATION 0 : L= 95.4116505377 DL= 2.28e+01 (AVERGE_DL)= 0.6441102921 ITERATION 1 : L= 96.9255354710 DL= 1.51e+00 (AVERGE_DL)= 0.1659071445 ITERATION 2 : L= 96.9704467257 DL= 4.49e-02 (AVERGE_DL)= 0.0285756586 ITERATION 3 : L= 96.9751943589 DL= 4.75e-03 (AVERGE_DL)= 0.0092908882 ITERATION 4 : L= 96.9756561226 DL= 4.62e-04 (AVERGE_DL)= 0.0028975339 ITERATION 5 : L= 96.9757054072 DL= 4.93e-05 (AVERGE_DL)= 0.0009466178 ITERATION 6 : L= 96.9757104834 DL= 5.08e-06 (AVERGE_DL)= 0.0003037977 ITERATION 7 : L= 96.9757110035 DL= 5.20e-07 (AVERGE_DL)= 0.0000972499 LOCALIZATION SUM CONVERGED ------------------------------------------------------ AUGMENTED HESSIAN OPTIMIZATION OF FOSTER-BOYS ORBITALS ------------------------------------------------------ Spin operator: 0 Orbital window: 4 to 14 Number of iterations: 128 Gradient tolerance: 1.000e-06 Number of pairs: 55 Davidson threshold: 2000 Diagonalization method: LAPACK Iter: 0 L: 96.9757110035 Grad. norm: 7.741194e-04 *** Likely close to a maximum now. *** Augmented Hessian eigenvalues: 1.19e-07 -1.51e+00 -2.53e+00 -3.32e+00 ... Iter: 1 L: 96.9757110632 Grad. norm: 5.660907e-08 LOCALIZATION HAS CONVERGED. Eigenvalues of the Hessian: 0 -1.507e+00 1 -2.532e+00 2 -3.317e+00 3 -5.025e+00 4 -5.499e+00 5 -7.040e+00 6 -7.415e+00 7 -1.788e+01 8 -1.799e+01 9 -1.887e+01 ... ------------------------------------------------------------------------------- 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 - 9 two center bond MO`s - 0 significantly delocalized MO`s Rather strongly localized orbitals: MO 5: 0O - 0.976563 MO 4: 0O - 0.964069 Bond-like localized orbitals: MO 14: 7H - 0.470781 and 5C - 0.536593 MO 13: 6H - 0.475128 and 5C - 0.537113 MO 12: 5C - 0.481318 and 2C - 0.515681 MO 11: 5C - 0.481318 and 2C - 0.515681 MO 10: 4H - 0.466376 and 2C - 0.545543 MO 9: 3H - 0.497333 and 1C - 0.543541 MO 8: 2C - 0.577817 and 1C - 0.475016 MO 7: 1C - 0.372874 and 0O - 0.629355 MO 6: 1C - 0.372874 and 0O - 0.629355 Localized MO's were stored in: acrolein_DLPNO_STEOM_CCSD.loc Localizing the core orbitals ------------------------------------------------------------------------------ ORCA ORBITAL LOCALIZATION ------------------------------------------------------------------------------ Input orbitals are from ... acrolein_DLPNO_STEOM_CCSD.loc Output orbitals are to ... acrolein_DLPNO_STEOM_CCSD.loc Max. number of iterations ... 128 Localizations seeded randomly ... off Convergence tolerance ... 1.000e-06 Using relative localization threshhold ... 1.000e-08 Treshold for strong local MOs ... 9.500e-01 Treshold for bond MOs ... 8.500e-01 Operator ... 0 Orbital range for localization ... 0 to 3 Localization criterion ... FOSTER-BOYS (AUGMENTED HESSIAN) Doing the dipole integrals ... o.k. Initial value of the localization sum : 26.671740 ITERATION 0 : L= 26.6717411784 DL= 7.94e-07 (AVERGE_DL)= 0.0003638392 LOCALIZATION SUM CONVERGED ------------------------------------------------------ AUGMENTED HESSIAN OPTIMIZATION OF FOSTER-BOYS ORBITALS ------------------------------------------------------ Spin operator: 0 Orbital window: 0 to 3 Number of iterations: 128 Gradient tolerance: 1.000e-06 Number of pairs: 6 Davidson threshold: 2000 Diagonalization method: LAPACK Iter: 0 L: 26.6717411784 Grad. norm: 2.059540e-05 *** Likely close to a maximum now. *** Augmented Hessian eigenvalues: 4.95e-12 -2.11e+01 -2.55e+01 -3.11e+01 ... Iter: 1 L: 26.6717411784 Grad. norm: 1.165557e-17 LOCALIZATION HAS CONVERGED. Eigenvalues of the Hessian: 0 -2.110e+01 1 -2.555e+01 2 -3.107e+01 3 -8.095e+01 4 -8.572e+01 5 -1.820e+02 ------------------------------------------------------------------------------- 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 - 4 strongly local MO`s - 0 two center bond MO`s - 0 significantly delocalized MO`s Rather strongly localized orbitals: MO 3: 5C - 0.999482 MO 2: 2C - 0.998440 MO 1: 1C - 1.001094 MO 0: 0O - 0.998704 Localized MO's were stored in: acrolein_DLPNO_STEOM_CCSD.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 -------------------------- CLOSED-SHELL FOCK OPERATOR -------------------------- Restoring SHARK [2] ... ok RI-JK section for the Fock operator: RHF full Fock operator ... (SHARK)done RHF frozen core Fock operator ... (SHARK)done Time needed for Fock operator ... 0.116 sec Reference energy ... -190.616589711 -------------- DLPNO SETTINGS (2015 fully linear scaling implementation) -------------- TCutMKN: 1.000e-03 TCutPAO: 1.000e-03 TCutPNO: 3.330e-07 TCutPNOSingles: 9.990e-09 TCutEN: 9.700e-01 TCutPAOExt: 1.000e-01 TCutPairs: 1.000e-04 TCutPre: 1.000e-06 TCutOSV: 1.000e-06 TCutDOij: 1.000e-05 TCutDO: 1.000e-02 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 -------------------------- 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-06 .... 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 ... 2.0e-02 TCutPairs ... 1.0e-04 TCutPNO_CrudeMP2 ... 3.3e-07 TCutPNOSingles_CrudeMP2 ... 1.0e-08 -------------------------------- LOCAL RI TRANSFORMATION (IAVPAO) -------------------------------- Orbital window: 4 to 14 Number of PAOs: 76 Basis functions: 76 (36 shells) Aux. functions: 248 (88 shells) Use SHARK: on Processing maps (0.0 sec) Average map sizes: Aux shells -> MOs 11.0 Aux shells -> PAOs 76.0 MOs -> AO shells 36.0 PAOs -> AO shells 36.0 Calculating integrals (0.1 sec, 1.585 MB) Sorting integrals (0.0 sec, 1.582 MB) Total time for the integral transformation: 0.1 sec -------------------------------- INITIAL GUESS AND PNO GENERATION -------------------------------- PNO truncation parameters .... PAOOverlapThresh = 1.000e-08 TCutPairs = 1.000e-04 TCutPNO = 3.330e-07 TCutPNOSingles = 9.990e-09 TCutMP2Pairs = 1.000e-05 TCutMKN = 1.000e-02 TCutDO = 2.000e-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 =========================== 62 OF 66 PAIRS ARE KEPT CCSD PAIRS 4 OF 66 PAIRS ARE KEPT MP2 PAIRS 0 OF 66 PAIRS ARE SKIPPED =========================== Total time spent in the initial guess ... 0.031 sec SL-MP2 correlation energy (all non-screened pairs) ... -0.546290835885 Eh Initial PNO correlation energy ... -0.545797815180 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 ... -0.000177134044 Eh sum of PNO error estimates for the kept pairs ... -0.000315886661 Eh -------------------- sum of all corrections -0.000493020705 Initial total correlation energy -0.546290835885 Thresholds for map construction and integral transformation for fine MP2 and CCSD(T) calculation: TCutMKN ... 1.0e-03 TCutDO ... 1.0e-02 TCutPairs ... 1.0e-04 TCutCMO ... 1.0e-03 TCutCPAO ... 1.0e-03 -------------------------------- LOCAL RI TRANSFORMATION (IAVPAO) -------------------------------- Orbital window: 4 to 14 Number of PAOs: 76 Basis functions: 76 (36 shells) Aux. functions: 248 (88 shells) Use SHARK: on Processing maps (0.0 sec) Average map sizes: Aux shells -> MOs 11.0 Aux shells -> PAOs 76.0 MOs -> AO shells 36.0 PAOs -> AO shells 36.0 Calculating integrals (0.1 sec, 1.585 MB) Sorting integrals (0.0 sec, 1.582 MB) Total time for the integral transformation: 0.1 sec -------------------------------- INITIAL GUESS AND PNO GENERATION -------------------------------- PNO truncation parameters .... PAOOverlapThresh = 1.000e-08 TCutPairs = 1.000e-04 TCutPNO = 3.330e-07 TCutPNOSingles = 9.990e-09 TCutMP2Pairs = 1.000e-05 TCutMKN = 1.000e-03 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 PNO Occupation Number Statistics: | Av. % of trace(Dij) retained ... 99.443830635786 | sigma^2 in % of trace(Dij) retained ... 1.31e+00 | Av. % of trace(Di) retained ... 99.999699673947 | sigma^2 in % of trace(Di) retained ... 7.95e-09 Distributions of % trace(Dij) recovered: | >= 99.9 ... 34 ( 51.5 % of all pairs) | [90.0, 99.0) ... 11 ( 16.7 % of all pairs) | [99.0, 99.9) ... 21 ( 31.8 % of all pairs) Distributions of % trace(Di) recovered : | >= 99.9 ... 11 (100.0 % of all I-pairs ) Making pair pair interaction lists ... done =========================== 62 OF 66 PAIRS ARE KEPT =========================== Total time spent in the initial guess ... 0.074 sec SL-MP2 correlation energy (all non-screened pairs) ... -0.546573063421 Eh Initial PNO correlation energy ... -0.546066476830 Eh sum of pair energies estimated for screened out pairs ... 0.000000000000 Eh sum of MP2 pair energies for pairs that were not kept ... -0.000176994495 Eh sum of PNO error estimates for the kept pairs ... -0.000329592097 Eh -------------------- sum of all corrections -0.000506586591 Initial total correlation energy -0.546573063421 Thresholds for map construction and integral transformation for fine MP2 and CCSD(T) calculation: TCutMKN ... 1.0e-03 TCutDO ... 1.0e-02 TCutPairs ... 1.0e-04 TCutCMO ... 1.0e-03 TCutCPAO ... 1.0e-03 Time for aux screen maps: 0.000 Time for maps after fine MP2: 0.001 ----------------------------- LOCAL RI TRANSFORMATION (IJV) ----------------------------- Orbital window: 4 to 14 Basis functions: 76 (36 shells) Aux. functions: 248 (88 shells) Use SHARK: on Processing maps (0.0 sec) Average map sizes: Aux shells -> MOs(i) 11.0 Aux shells -> MOs(j) 11.0 MOs -> AO shells 36.0 Calculating integrals (0.1 sec, 0.232 MB) Sorting integrals (0.0 sec, 0.229 MB) Total time for the integral transformation: 0.1 sec -------------------------------- LOCAL RI TRANSFORMATION (VABPAO) -------------------------------- Number of PAOs: 76 Basis functions: 76 (36 shells) Aux. functions: 248 (88 shells) Use SHARK: on Processing maps (0.0 sec) Average map sizes: Aux shells -> PAOs 76.0 PAOs -> AO shells 36.0 Calculating integrals (0.1 sec, 10.932 MB) Finished ------------------------------------- Pair Pair Term precalculation with RI-(ij|mn) and (im|jn) transformation ON THE FLY ------------------------------------- IBatch 1 (of 1) ... done ( 0.598 sec) Total EXT ... 0.598 sec --------------------- RI-PNO TRANSFORMATION --------------------- Total Number of PNOs ... 1434 Average number of PNOs per pair ... 23 Maximal number of PNOs per pair ... 35 #pairs with 1 - 5 PNOs : 0 #pairs with 6 - 10 PNOs : 0 #pairs with 11 - 15 PNOs : 7 #pairs with 16 - 20 PNOs : 12 #pairs with 21 - 25 PNOs : 22 #pairs with 26 - 30 PNOs : 18 #pairs with 31 - 35 PNOs : 3 #pairs with 36 - 40 PNOs : 0 #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 ... 0.262 sec Size of the 3-external file ... 6 MB Size of the 4-external file ... 23 MB Size of the IKJL file ... 0 MB Size of the all 3-external file ... 37 MB Size of the 1-external file ... 0 MB --------------------------------- RI-PNO TRANSFORMATION FOR SINGLES --------------------------------- Total Number of singles PNOs ... 374 Average number of PNOs per singles pair ... 34 Maximal number of singles PNOs per pair ... 47 #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 : 4 #pairs with 31 - 35 PNOs : 4 #pairs with 36 - 40 PNOs : 0 #pairs with 41 - 45 PNOs : 1 #pairs with 46 - 50 PNOs : 2 Generation of (ia|bc)[P] integrals for singles ... on Ibatch: 1 (of 1) Starting 2-4 index PNO integral generation ... done Making pair/pair overlap matrices ... done ( 0.031 sec) Size of the pair overlap file ... 12 MB Redoing the guess amplitudes ... done ( 0.002 sec) ------------------------- FINAL STARTUP INFORMATION ------------------------- E(0) ... -190.616589711 E(SL-MP2) ... -0.546573063 E(SL-MP2) including corrections ... -0.546573063 Initial E(tot) ... -191.163162774 ... 0.165108472 Number of pairs included ... 62 Total number of pairs ... 66 ------------------------------------------------ RHF COUPLED CLUSTER ITERATIONS ------------------------------------------------ Number of PNO amplitudes to be optimized ... 34644 Number of non-PNO amplitudes ... 230702 Untruncated number of regular amplitudes ... 245586 Iter E(tot) E(Corr) Delta-E Residual Time 0 -191.163168466 -0.546072168 0.000500895 0.019012574 0.74 *** Turning on DIIS *** 1 -191.194681868 -0.577585570 -0.031513402 0.015233958 0.87 2 -191.214699946 -0.597603648 -0.020018078 0.008338943 0.80 3 -191.219258199 -0.602161901 -0.004558253 0.004942662 0.75 4 -191.221299078 -0.604202780 -0.002040879 0.002062898 0.83 5 -191.221989745 -0.604893447 -0.000690667 0.000657239 0.79 6 -191.222091195 -0.604994897 -0.000101450 0.000307187 0.74 7 -191.222098082 -0.605001784 -0.000006887 0.000155099 0.78 8 -191.222109776 -0.605013478 -0.000011694 0.000058056 0.81 9 -191.222105680 -0.605009382 0.000004096 0.000021489 0.76 10 -191.222107782 -0.605011484 -0.000002102 0.000008652 0.75 --- The Coupled-Cluster iterations have converged --- ---------------------- COUPLED CLUSTER ENERGY ---------------------- E(0) ... -190.616589711 E(CORR)(strong-pairs) ... -0.605011484 E(CORR)(weak-pairs) ... -0.000506587 E(CORR)(corrected) ... -0.605518071 E(TOT) ... -191.222107782 Singles Norm **1/2 ... 0.071078437 T1 diagnostic ... 0.015153974 ------------------ LARGEST AMPLITUDES ------------------ 7-> 15 7-> 15 0.061674 6-> 15 6-> 15 0.061674 11-> 15 11-> 15 0.055351 12-> 15 12-> 15 0.055351 7-> 15 6-> 15 0.053205 12-> 15 11-> 15 0.049349 9-> 16 9-> 16 0.038507 13-> 16 13-> 16 0.035116 14-> 16 14-> 16 0.034583 10-> 16 10-> 16 0.033646 14-> 22 14-> 22 0.033239 9-> 21 9-> 21 0.031585 13-> 23 13-> 23 0.031186 10-> 22 10-> 22 0.029774 7-> 15 -1-> -1 0.029509 6-> 15 -1-> -1 0.029509 !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! ! Warning: Linearized densities requested! These are not the proper ! ! density matrices for non-variational theories, e.g., CCSD, QCISD. ! ! It is better to use the Density = Unrelaxed option in the input. ! !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! NORM = 1.238029296 sqrt= 1.112667649 W(HF) = 0.807735328 ------------------------------------------------------------------------------ ORCA POPULATION ANALYSIS ------------------------------------------------------------------------------ Input electron density ... acrolein_DLPNO_STEOM_CCSD.mdcip BaseName (.gbw .S,...) ... acrolein_DLPNO_STEOM_CCSD ---------------------- ACTIVE SPACE SELECTION ---------------------- Calculating the RI metric ... done WARNING: NRootsCISNAT (0) is lower than NRoots (5). I will take NRootsCISNAT = 5. ------------------- RHF CIS CALCULATION ------------------- Number of roots to be optimized ... 5 Number of amplitudes to be optimized ... 671 Building the initial guess ... done Iter Delta-E Residual ------------------------------------------------------- 0 0.412225452604 0.027432453882 1 0.033303590221 0.001757762677 2 0.006086554670 0.002133690193 3 0.003850799019 0.000782346432 4 0.002297112517 0.001122215277 5 0.001610338010 0.000525612725 6 0.001195837616 0.000644101927 7 0.000901719779 0.000333866185 8 0.000701659537 0.000371338924 9 0.000528262741 0.000184476559 10 0.000410875061 0.000215401519 11 0.000300087948 0.000141120864 12 0.000305522828 0.000239214012 13 0.000296692140 0.000132561948 14 0.000314212790 0.000235011975 15 0.000295588354 0.000093641827 16 0.000299522197 0.000224558728 17 0.000276596101 0.000071633885 18 0.000282742089 0.000230229181 19 0.000256988625 0.000057424018 20 0.000264622003 0.000249831771 21 0.000236593303 0.000046298773 22 0.000246660533 0.000271977783 23 0.000215797625 0.000036403644 24 0.000225126288 0.000281513619 25 0.000190861639 0.000027298528 26 0.000194957936 0.000266841269 27 0.000158355405 0.000019102728 28 0.000154458202 0.000225734985 29 0.000118906558 0.000012063900 30 0.000107924736 0.000166156769 31 0.000078222564 0.000006608014 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The CIS iterations have converged --- ----------- CIS RESULTS ----------- IROOT= 1: 0.170527 au 4.640 eV 37426.3 cm**-1 13 -> 15 0.765789 (-0.875094) 13 -> 18 0.192045 (-0.438229) IROOT= 2: 0.272239 au 7.408 eV 59749.6 cm**-1 13 -> 16 0.010910 (-0.104452) 14 -> 15 0.928769 (-0.963727) IROOT= 3: 0.328057 au 8.927 eV 72000.2 cm**-1 9 -> 15 0.012350 ( 0.111129) 9 -> 18 0.013659 ( 0.116874) 10 -> 15 0.039939 ( 0.199846) 11 -> 15 0.673985 (-0.820966) 11 -> 18 0.021003 ( 0.144923) 13 -> 15 0.070759 (-0.266006) 13 -> 18 0.133028 ( 0.364729) IROOT= 4: 0.344992 au 9.388 eV 75717.0 cm**-1 8 -> 18 0.079159 ( 0.281352) 9 -> 15 0.041339 (-0.203321) 9 -> 18 0.010001 (-0.100004) 10 -> 15 0.678657 (-0.823807) 10 -> 18 0.013286 (-0.115264) 11 -> 15 0.091628 (-0.302702) 11 -> 18 0.018785 ( 0.137058) 13 -> 18 0.021232 (-0.145711) 14 -> 16 0.011692 ( 0.108129) IROOT= 5: 0.362696 au 9.869 eV 79602.5 cm**-1 11 -> 15 0.010422 ( 0.102089) 12 -> 17 0.017408 (-0.131939) 14 -> 16 0.054979 (-0.234476) 14 -> 17 0.854536 (-0.924411) 14 -> 19 0.021305 ( 0.145964) -------------------------------------------------------------------- UNRELAXED EXCITED STATE DIPOLE MOMENTS -------------------------------------------------------------------- E(eV) DX(au) DY(au) DZ(au) |D|(D) IROOT= 1: 4.640 0.086587 -0.076752 -0.000000 0.294104 IROOT= 2: 7.408 1.208418 1.561312 0.000000 5.018343 IROOT= 3: 8.927 1.057838 0.950748 -0.000000 3.615205 IROOT= 4: 9.388 0.513987 0.521468 -0.000000 1.861095 IROOT= 5: 9.869 1.651205 -1.430209 -0.000000 5.552520 -------------------------------------------------------------------- ------------------------------------------ NATURAL ORBITALS FOR STATE 1 ------------------------------------------ Making the (pseudo)densities ... done ------------------------------------------ NATURAL ORBITALS FOR STATE 2 ------------------------------------------ Making the (pseudo)densities ... done ------------------------------------------ NATURAL ORBITALS FOR STATE 3 ------------------------------------------ Making the (pseudo)densities ... done ------------------------------------------ NATURAL ORBITALS FOR STATE 4 ------------------------------------------ Making the (pseudo)densities ... done ------------------------------------------ NATURAL ORBITALS FOR STATE 5 ------------------------------------------ Making the (pseudo)densities ... done ------------------------------------------ STATE AVERAGED NATURAL ORBITALS FOR ACTIVE SPACE SELECTION ------------------------------------------ Solving eigenvalue problem for the occupied space ... done Solving eigenvalue problem for the virtual space ... done After automatic selection of the active space: No of roots active in IP calculation: 8 No of roots active in EA calculation: 7 Testing the validity of the selected OCC active space ... --- complex eigenvalues and eigenvectors OK ! Testing the validity of the selected VIRT active space ... --- complex eigenvalues and eigenvectors OK ! After auto-adaptation of the active space: No of roots active in IP calculation: 8 No of roots active in EA calculation: 7 done ( 0.7) --------------------------------------------------- RHF EOM-DLPNO-CCSD CALCULATION --------------------------------------------------- EOM type ... IP-EOM Eigenvectors ... RHS Solver ... Davidson K(R) Formation ... MO Convergence check ... for each root separately Convergence threshold ... 1.00E-05 Root homing ... on Preconditioning update ... CIS Reduced space size (times number of roots) ... 40 Number of roots in the CIS initial guess ... 8 Number of roots to be optimized ... 8 Solving roots ... separately Number of amplitudes to be optimized ... 7392 -------------------------------- AUTOMATIC CHOICE OF INCORE LEVEL -------------------------------- Memory available ... 3953.39 MB Memory needed for Residual-vectors ... 0.02 MB Memory needed for Ritz-vectors ... 0.17 MB Memory needed for Sigma-vectors ... 0.85 MB Memory needed for State-vectors ... 0.85 MB -> Final InCoreLevel ... 5 Dressing integrals for EOM-DLPNO-CCSD ... done ( 0.1) Building the initial guess ... done ( 0.0) BATCH 1 OF 8 Iter Delta-E Residual Time --------------------------------------------------- 0 0.472380210325 0.049729565565 0.211 1 0.067424101049 0.003146576536 0.220 2 0.004247258385 0.000607722034 0.235 3 0.000682736447 0.000189838464 0.235 4 0.000198357551 0.000089763920 0.263 5 0.000087525878 0.000047477359 0.248 6 0.000020886267 0.000017100650 0.285 7 0.000007347821 0.000002887374 0.227 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The EOM iterations have converged --- BATCH 2 OF 8 Iter Delta-E Residual Time --------------------------------------------------- 0 0.495803699026 0.097026788158 0.218 1 0.118658377380 0.005537131564 0.210 2 0.009926057385 0.001332250011 0.233 3 0.002129745818 0.000578148535 0.233 4 0.001038124608 0.000175321009 0.254 5 0.000007485224 0.000042540647 0.250 6 0.000136774493 0.000011500705 0.273 7 0.000016770957 0.000002638591 0.225 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The EOM iterations have converged --- BATCH 3 OF 8 Iter Delta-E Residual Time --------------------------------------------------- 0 0.623106777533 0.072172684716 0.215 1 0.091945717767 0.007101769129 0.215 2 0.010665145098 0.002445432389 0.235 3 0.004037198587 0.001061607679 0.234 4 0.002155243059 0.000812174563 0.239 5 0.007085160308 0.012013122934 0.265 6 0.009397225781 0.000755742693 0.280 7 0.000903761832 0.000133184345 0.273 8 0.000206099626 0.000026961830 0.292 9 0.000059863057 0.000008151152 0.240 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The EOM iterations have converged --- BATCH 4 OF 8 Iter Delta-E Residual Time --------------------------------------------------- 0 0.608112221416 0.058288965642 0.212 1 0.084321667848 0.004598816055 0.215 2 0.009197306650 0.001113676121 0.227 3 0.004023372018 0.002738016749 0.240 4 0.007489690954 0.003396169590 0.249 5 0.002968465576 0.000627485608 0.269 6 0.001173399860 0.000270164255 0.275 7 0.000354733900 0.000133868430 0.274 8 0.000105982177 0.000062853340 0.292 9 0.000018274651 0.000018453925 0.295 10 0.000008549839 0.000006687022 0.256 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The EOM iterations have converged --- BATCH 5 OF 8 Iter Delta-E Residual Time --------------------------------------------------- 0 0.668940221711 0.085435263941 0.207 1 0.097215671086 0.011803169686 0.225 2 0.025177099509 0.001939749976 0.223 3 0.002811274588 0.001129855502 0.242 4 0.004418172733 0.002454889005 0.247 5 0.010886777892 0.007171486601 0.260 6 0.007608982594 0.001509807975 0.268 7 0.001518824141 0.000625804830 0.279 8 0.001264367237 0.000261559158 0.278 9 0.000024557935 0.000080042215 0.303 10 0.000254019761 0.000046230784 0.298 11 0.000001769974 0.000179899035 0.317 12 0.000190437110 0.002171961929 0.333 13 0.000234691431 0.000064882952 0.329 14 0.000144581820 0.000011788698 0.348 15 0.000037633983 0.000002634034 0.292 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The EOM iterations have converged --- BATCH 6 OF 8 Iter Delta-E Residual Time --------------------------------------------------- 0 0.718511334220 0.071119777563 0.210 1 0.099392276261 0.007153370961 0.217 2 0.013385969294 0.002423455905 0.228 3 0.007873614688 0.004221575675 0.236 4 0.008657060190 0.003657691497 0.251 5 0.005408842809 0.000854612321 0.257 6 0.003079225081 0.001667372772 0.274 --- complex eigenvalues and eigenvectors 7 0.012731001324 0.011669523861 0.287 8 0.008136267582 0.000715383895 0.281 9 0.000958398265 0.000185976042 0.302 10 0.000430922358 0.000160120793 0.305 11 0.000881382939 0.001327563743 0.333 12 0.001929889777 0.000701819177 0.339 13 0.000640010445 0.000077254875 0.332 14 0.000025834028 0.000015882814 0.360 15 0.000000401731 0.000003952999 0.281 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The EOM iterations have converged --- BATCH 7 OF 8 Iter Delta-E Residual Time --------------------------------------------------- 0 0.745145558498 0.092648532439 0.201 1 0.081520323023 0.031788028055 0.218 2 0.060778147286 0.003288781070 0.231 3 0.005800968587 0.001311284016 0.236 4 0.008281044813 0.009870352669 0.255 5 0.012046551831 0.002843272164 0.253 6 0.005700400206 0.001282021732 0.274 7 0.002319108836 0.007020771591 0.285 8 0.008371398398 0.002277366177 0.284 9 0.002611913273 0.000381193667 0.299 10 0.000369992181 0.000093650758 0.296 11 0.000233815747 0.000028854902 0.324 12 0.000313494047 0.000029187187 0.342 --- complex eigenvalues and eigenvectors 13 0.000423082842 0.026290054897 0.329 14 0.000645389464 0.000028811717 0.350 15 0.000062790118 0.000007238230 0.280 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The EOM iterations have converged --- BATCH 8 OF 8 Iter Delta-E Residual Time --------------------------------------------------- 0 0.851759527291 0.069514369637 0.209 1 0.008202262405 0.066013290733 0.216 2 0.106567867420 0.036526535726 0.234 3 0.115430045912 0.081555517848 0.231 4 0.104818748765 0.041455978806 0.261 5 0.088007851959 0.071044987315 0.249 6 0.114400085821 0.009036142380 0.279 7 0.026352901781 0.011802836955 0.282 8 0.031206789968 0.010419393996 0.288 9 0.017536006564 0.005296615250 0.305 10 0.009880498428 0.007393232840 0.298 11 0.010731563279 0.002599565762 0.325 12 0.016943440587 0.018435323617 0.340 13 0.015306152829 0.001640635406 0.333 14 0.001780512777 0.000870136490 0.351 15 0.020906198199 0.042343345090 0.364 16 0.019519490909 0.000979176438 0.367 17 0.000863747368 0.000216571852 0.379 18 0.000146278578 0.000048764494 0.399 19 0.000061698428 0.000013151020 0.413 20 0.000021347391 0.000003809501 0.305 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The EOM iterations have converged --- ---------------------- EOM-CCSD RESULTS (RHS) ---------------------- IROOT= 1: 0.399712 au 10.877 eV 87726.6 cm**-1 Amplitude Excitation -0.696916 14 -> x Percentage singles character= 96.85 IROOT= 2: 0.364179 au 9.910 eV 79928.0 cm**-1 Amplitude Excitation 0.687476 13 -> x Percentage singles character= 98.56 IROOT= 3: 0.515446 au 14.026 eV 113127.3 cm**-1 Amplitude Excitation -0.687394 12 -> x Percentage singles character= 96.12 IROOT= 4: 0.513447 au 13.972 eV 112688.6 cm**-1 Amplitude Excitation 0.687063 11 -> x Percentage singles character= 95.82 IROOT= 5: 0.539850 au 14.690 eV 118483.5 cm**-1 Amplitude Excitation 0.108210 8 -> x 0.134391 9 -> x -0.666478 10 -> x Percentage singles character= 97.19 IROOT= 6: 0.601617 au 16.371 eV 132039.7 cm**-1 Amplitude Excitation 0.374315 8 -> x -0.568873 9 -> x Percentage singles character= 94.69 IROOT= 7: 0.598261 au 16.280 eV 131303.2 cm**-1 Amplitude Excitation -0.573024 8 -> x -0.338213 9 -> x -0.175315 10 -> x Percentage singles character= 94.85 IROOT= 8: 0.708118 au 19.269 eV 155414.0 cm**-1 Amplitude Excitation -0.683852 7 -> x Percentage singles character= 93.75 IP STATE= 0: percentage singles 96.851 IP STATE= 1: percentage singles 98.559 IP STATE= 2: percentage singles 96.123 IP STATE= 3: percentage singles 95.820 IP STATE= 4: percentage singles 97.192 IP STATE= 5: percentage singles 94.694 IP STATE= 6: percentage singles 94.852 IP STATE= 7: percentage singles 93.749 Final no active IP roots: 8 EOMIP-CCSD done in ( 29.5) --------------------------------------------------- RHF EOM-DLPNO-CCSD CALCULATION --------------------------------------------------- EOM type ... EA-EOM Eigenvectors ... RHS Solver ... Davidson K(R) Formation ... MO Convergence check ... for each root separately Convergence threshold ... 1.00E-05 Root homing ... on Preconditioning update ... CIS Reduced space size (times number of roots) ... 40 Number of roots in the CIS initial guess ... 7 Number of roots to be optimized ... 7 Solving roots ... separately Number of amplitudes to be optimized ... 40992 -------------------------------- AUTOMATIC CHOICE OF INCORE LEVEL -------------------------------- Memory available ... 1951.59 MB Memory needed for 3-ext integrals ... 0.82 MB Memory needed for 4-ext integrals ... 8.44 MB Memory needed for Residual-vectors ... 0.10 MB Memory needed for Ritz-vectors ... 0.71 MB Memory needed for Sigma-vectors ... 4.08 MB Memory needed for State-vectors ... 4.08 MB -> Final InCoreLevel ... 5 Dressing integrals for EOM-DLPNO-CCSD ... done ( 0.1) Building the initial guess ... done ( 0.0) BATCH 1 OF 7 Iter Delta-E Residual Time --------------------------------------------------- 0 0.143288693716 0.104549678617 0.244 1 0.090506148445 0.003629371013 0.250 2 0.008360964328 0.000317706968 0.260 3 0.000431836331 0.000033373834 0.244 4 0.000039555369 0.000009271431 0.223 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The EOM iterations have converged --- BATCH 2 OF 7 Iter Delta-E Residual Time --------------------------------------------------- 0 0.223693673996 0.051542106583 0.202 1 0.049945880209 0.002121027616 0.208 2 0.005961394367 0.000290288516 0.230 3 0.000685092317 0.000170357878 0.219 4 0.000726940663 0.000597889351 0.248 5 0.000899537198 0.001041172949 0.240 6 0.006618700202 0.000595872406 0.312 7 0.000336432189 0.000377358006 0.272 8 0.000801924310 0.000090872813 0.282 9 0.000078914027 0.000012588387 0.262 10 0.000110844648 0.000001845946 0.229 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The EOM iterations have converged --- BATCH 3 OF 7 Iter Delta-E Residual Time --------------------------------------------------- 0 0.240828348289 0.069812185460 0.193 1 0.067501799022 0.003088610061 0.240 2 0.007953204346 0.000464430185 0.198 3 0.000469023523 0.000326549928 0.231 4 0.000583028848 0.000268458972 0.250 5 0.000044623553 0.000153219464 0.259 6 0.000466376906 0.000281653116 0.261 7 0.000886480448 0.000279851985 0.303 8 0.000225768908 0.000061349645 0.299 9 0.000142453500 0.000008391894 0.267 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The EOM iterations have converged --- BATCH 4 OF 7 Iter Delta-E Residual Time --------------------------------------------------- 0 0.299788136373 0.133911116840 0.194 1 0.118252558390 0.009724517967 0.224 2 0.064771181297 0.075114389749 0.212 3 0.065432555838 0.007609084816 0.239 4 0.008827412581 0.000496790088 0.233 5 0.000277578360 0.000061755408 0.251 --- complex eigenvalues and eigenvectors 6 0.000430998903 0.000015049959 0.257 --- complex eigenvalues and eigenvectors 7 0.000060457627 0.000003387420 0.257 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The EOM iterations have converged --- BATCH 5 OF 7 Iter Delta-E Residual Time --------------------------------------------------- 0 0.398482105552 0.139445733884 0.237 1 0.009302401398 0.145318230355 0.229 2 0.162193217415 0.018686475193 0.240 3 0.234570681646 0.303620526943 0.228 4 0.054669876419 0.251044477376 0.233 5 0.072809973240 0.395194186612 0.233 6 0.401395480492 0.010728096836 0.252 7 0.031797366840 0.012573572423 0.258 8 0.010548828115 0.004243600881 0.282 9 0.003489466064 0.000541763214 0.264 10 0.000908882695 0.000347012962 0.315 --- complex eigenvalues and eigenvectors 11 0.000803297317 0.000187797629 0.322 12 0.000274277219 0.000038849010 0.287 13 0.000045785148 0.000005510078 0.248 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The EOM iterations have converged --- BATCH 6 OF 7 Iter Delta-E Residual Time --------------------------------------------------- 0 0.602381453529 0.171476418835 0.192 1 0.002782224599 0.183917425900 0.208 2 0.073588413133 0.217022615397 0.206 3 0.004707665603 0.234314825972 0.230 4 0.001798839789 0.197750200586 0.244 5 0.119434456651 0.180086007357 0.237 6 0.338286497202 0.075967728709 0.286 7 0.024040139526 0.025220807809 0.270 8 0.016947259983 0.048800579630 0.278 9 0.056121870006 0.045798738406 0.284 10 0.000168676832 0.047756209239 0.268 11 0.000226505011 0.020698195722 0.296 12 0.002389080886 0.002396060986 0.282 13 0.002107230483 0.000349768297 0.306 14 0.000728456404 0.000070952099 0.298 15 0.000087219106 0.000011354946 0.359 16 0.000003584467 0.000002891787 0.289 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The EOM iterations have converged --- BATCH 7 OF 7 Iter Delta-E Residual Time --------------------------------------------------- 0 0.718768364560 0.204348474732 0.189 1 0.169709132818 0.169144361930 0.206 2 0.361990296864 0.075164622164 0.209 3 0.084526536164 0.007724228214 0.219 4 0.007783063554 0.005317444897 0.229 5 0.002442012121 0.006165907061 0.224 6 0.015320188642 0.008334044680 0.250 7 0.002194177110 0.003325803779 0.244 8 0.007585874229 0.002647075284 0.312 9 0.000054087122 0.003010896117 0.283 10 0.003246239553 0.000347116409 0.292 11 0.000670029303 0.000145724473 0.277 12 0.000152392997 0.000075284237 0.278 13 0.000001991767 0.000114511186 0.300 14 0.000033300404 0.000021993533 0.288 15 0.000021126180 0.000007423095 0.261 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The EOM iterations have converged --- ---------------------- EOM-CCSD RESULTS (RHS) ---------------------- IROOT= 1: 0.043950 au 1.196 eV 9646.0 cm**-1 Amplitude Excitation -0.696348 x -> 15 Percentage singles character= 94.68 IROOT= 2: 0.170923 au 4.651 eV 37513.3 cm**-1 Amplitude Excitation 0.700521 x -> 17 Percentage singles character= 97.03 IROOT= 3: 0.162645 au 4.426 eV 35696.4 cm**-1 Amplitude Excitation -0.700522 x -> 16 Percentage singles character= 96.95 IROOT= 4: 0.171399 au 4.664 eV 37617.7 cm**-1 Amplitude Excitation 0.692484 x -> 18 Percentage singles character= 93.40 IROOT= 5: 0.221973 au 6.040 eV 48717.5 cm**-1 Amplitude Excitation 0.689729 x -> 19 -0.116555 x -> 20 Percentage singles character= 97.04 IROOT= 6: 0.399452 au 10.870 eV 87669.6 cm**-1 Amplitude Excitation 0.688097 x -> 22 Percentage singles character= 94.98 IROOT= 7: 0.442621 au 12.044 eV 97144.0 cm**-1 Amplitude Excitation 0.692152 x -> 23 Percentage singles character= 95.29 EA STATE= 0: percentage singles 94.682 EA STATE= 1: percentage singles 97.029 EA STATE= 2: percentage singles 96.949 EA STATE= 3: percentage singles 93.399 EA STATE= 4: percentage singles 97.041 EA STATE= 5: percentage singles 94.980 EA STATE= 6: percentage singles 95.292 Final no active EA roots: 7 EOMEA-CCSD done in ( 20.9) *** Conversion of amplitudes and coefficient from local/PNO basis to NO basis *** Preparation for recanonicalization done in ( 0.0) Conversion of coefficients ... Conversion done in ( 0.0) Update of the Fock Matrix ... Updated Fock matrix in ( 0.0) Update of orbital energies ... done ---------------------------- Integral TRANSFORMATION -------------------------- <<<<< W A R N I N G >>>>> PNOSigmaOpt 0 is only possible for coupled pair type LPNO methods! --->>> changing to PNOSigmaOpt 2 -------------------- RI-METRIC GENERATION -------------------- Time for V**-1/2 generation: 0.139 sec ----------------- RI-TRANSFORMATION (AUX index driven) ----------------- Dimension of the orbital-basis ... 76 Dimension of the aux-basis ... 374 Transformation of internal MOs ... 4- 14 Transformation of internal/external MOs... 4- 14 to 15- 75 Number Format for Storage ... Double (8 Byte) Integral mode ... Direct First Phase: integral generation and transformation of MO indices Aux angular momentum 0 ... done ( 0.003 sec) Aux angular momentum 1 ... done ( 0.005 sec) Aux angular momentum 2 ... done ( 0.004 sec) Aux angular momentum 3 ... done ( 0.002 sec) Aux angular momentum 4 ... done ( 0.002 sec) Closing buffer VIJ ( 0.00 GB; CompressionRatio= 0.98) Closing buffer VIA ( 0.00 GB; CompressionRatio= 1.00) Phase 1 completed in 0.131 sec Second Phase: sorting and transformation of aux index IJ-Transformation Memory available ... 4000 MB Max. # MO pairs treated in a batch ... 2 # of internal orbitals ... 11 # batches for internal orbitals ... 1 Closing buffer IJV ( 0.00 GB; CompressionRatio= 1.00) (ij|v) transformation done in 0.009 sec IA-Transformation Memory available ... 4000 MB Max. # MO pairs treated in a batch ... 2 # of internal orbitals ... 11 # batches for internal orbitals ... 1 Closing buffer IAV ( 0.00 GB; CompressionRatio= 1.00) (ia|v) transformation done in 0.010 sec Phase 2 completed in 0.061 sec RI-Integral transformation completed in 0.198 sec ----------------------- RI-FORMATION OF (ik|jl) ----------------------- Max core memory to be used ... 4000 MB Memory needed per MO ... 0.0 MB # of MOs treated in a batch ... 2 # of batches needed ... 1 Data format used ... DOUBLE done ( 0.012 sec) Closing buffer KIJ ( 0.00 GB; CompressionRatio= 0.99) (ik|jl) transformation completed in 0.028 sec ----------------------- RI-FORMATION OF (ik|ja) ----------------------- Max core memory to be used ... 4000 MB Memory needed per MO ... 0.0 MB # of MOs treated in a batch ... 2 # of batches needed ... 1 Data format used ... DOUBLE done ( 0.005 sec) Closing buffer KIJ ( 0.00 GB; CompressionRatio= 1.00) (ik|ja) transformation completed in 0.019 sec ----------------------- RI-FORMATION OF (ij|ka) ----------------------- Max core memory to be used ... 4000 MB Memory needed per MO pair ... 0.0 MB # of MO pairs included in trafo ... 66 # of MO pairs treated in a batch ... 9 # of batches needed ... 1 Data format used ... DOUBLE done ( 0.003 sec) Closing buffer JIJ ( 0.00 GB; CompressionRatio= 1.00) (ij|ka) transformation completed in 0.016 sec ----------------------- RI-FORMATION OF (ia|jb) ----------------------- Max core memory to be used ... 4000 MB Memory needed per MO ... 0.2 MB # of MOs treated in a batch ... 3 # of batches needed ... 1 Data format used ... DOUBLE done ( 0.007 sec) Closing buffer KIJ ( 0.00 GB; CompressionRatio= 1.00) (ia|jb) transformation completed in 0.009 sec ------------------------------ INTEGRAL RI-(ij|ab) ------------------------------ Orbital Window ... 4.. 14 - 15.. 75 Memory available ... 4000 MB Reading internal integrals ... done ( 0.001 sec) Generating and transforming integrals ... Aux angular momentum 0 ... done ( 0.003 sec) Aux angular momentum 1 ... done ( 0.003 sec) Aux angular momentum 2 ... done ( 0.005 sec) Aux angular momentum 3 ... done ( 0.002 sec) Aux angular momentum 4 ... done ( 0.001 sec) (v|ab) ... done ( 0.015 sec) Orthogonalizing and resorting integrals... (a|vb) ... done ( 0.026 sec) Generating ij|ab ... (ij|ab) ... done ( 0.007 sec) (ij|ab) transformation completed in 0.170 sec Closing buffer IJAB[0] ( 0.00 GB; CompressionRatio= 1.00) Integral transformation done in ( 0.6) Making IJABD,IAJBD ... done ( 0.1) Performing recanonicalization Recanonicalization of T (ground state) amplitudes ... T amplitudes recanonicalization done in ( 0.0) Recanonicalization of IP amplitudes ... IP amplitudes recanonicalization done in ( 0.1) Recanonicalization of EA amplitudes ... EA amplitudes recanonicalization done in ( 0.1) Making FD ... done ( 0.3) Making IKJADs,IKJAD ... done ( 0.0) --------------------------------------------------- RHF STEOM-CCSD CALCULATION --------------------------------------------------- EOM type ... STEOM Multiplicity ... singlet Solver ... Davidson Convergence check ... for each root separately Convergence threshold ... 1.00E-05 Root homing ... on Preconditioning update ... CIS Reduced space size (times number of roots) ... 40 Number of roots in the CIS initial guess ... 200 Number of roots to be optimized ... 5 Number of amplitudes to be optimized ... 671 -------------------------------- AUTOMATIC CHOICE OF INCORE LEVEL -------------------------------- Memory available ... 4000.00 MB Memory needed for SIP and SEA amplitudes ... 2.64 MB -> Final InCoreLevel ... 1 Making SIP amplitudes for STEOM-CCSD ... done ( 3.3) Making SEA amplitudes for STEOM-CCSD ... done ( 0.6) Dressing integrals for STEOM-CCSD ... Dressing of Occ / Occ block ... done ( 0.0) Dressing of Virt / Virt block ... done ( 0.0) --------------------- CHAIN OF SPHERES GRID --------------------- 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 ... 10542 Total number of batches ... 169 Average number of points per batch ... 62 Average number of grid points per atom ... 1318 UseSFitting ... on done ( 71.4) done ( 3.5) Building the initial guess ... done ( 0.0) Solving Root No 1 Iter Delta-E Residual Time --------------------------------------------------- 0 0.144984549764 0.003266977443 0.003 1 0.003471573271 0.000179314591 0.003 2 0.000675580403 0.000047316748 0.004 3 0.000106362623 0.000003034015 0.003 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The STEOM iterations have converged --- Solving Root No 2 Iter Delta-E Residual Time --------------------------------------------------- 0 0.267913566755 0.006317426112 0.003 1 0.004404861882 0.000422990391 0.003 2 0.001210609618 0.000313502097 0.003 3 0.000932008477 0.000070615526 0.003 4 0.000250452615 0.000011494517 0.003 5 0.000050665768 0.000003247693 0.004 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The STEOM iterations have converged --- Solving Root No 3 Iter Delta-E Residual Time --------------------------------------------------- 0 0.296885104382 0.002331992052 0.003 1 0.002851655410 0.001599046493 0.003 2 0.005037240319 0.001671577699 0.003 3 0.007775274187 0.002244871946 0.003 4 0.006502887894 0.000847172250 0.003 5 0.002614149041 0.000477178929 0.004 6 0.000446057168 0.000092198922 0.003 7 0.000132173072 0.000027112078 0.003 8 0.000042514420 0.000003944351 0.003 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The STEOM iterations have converged --- Solving Root No 4 Iter Delta-E Residual Time --------------------------------------------------- 0 0.323930538758 0.004103537431 0.003 1 0.005173259485 0.001025851952 0.003 2 0.003648123798 0.001632711311 0.003 3 0.004552589245 0.000814660419 0.004 4 0.003861207827 0.000957601391 0.003 5 0.009098827667 0.002547132277 0.002 6 0.003042027851 0.000466169062 0.003 7 0.001563033795 0.000218139445 0.003 8 0.000272286678 0.000040297166 0.003 9 0.000090112386 0.000119498171 0.004 10 0.001407903650 0.000791142049 0.002 11 0.003410676760 0.000386308176 0.003 12 0.000787460225 0.000029999156 0.004 13 0.000152940883 0.000007351859 0.003 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The STEOM iterations have converged --- Solving Root No 5 Iter Delta-E Residual Time --------------------------------------------------- 0 0.362265390201 0.000624116072 0.003 1 0.001326049424 0.000203684856 0.003 2 0.001875631912 0.001020270254 0.003 3 0.001306408542 0.000152906679 0.003 4 0.005845558681 0.012076927639 0.003 5 0.005397231586 0.000088121836 0.003 6 0.000223748942 0.000088193637 0.003 7 0.000390006262 0.000334133157 0.003 8 0.000835692204 0.000238181649 0.004 9 0.000432145960 0.000081180464 0.003 10 0.000327739800 0.000170307963 0.003 11 0.000262119817 0.000048935837 0.003 12 0.000336266210 0.000173022275 0.004 13 0.000731092237 0.000287297177 0.003 14 0.002557503687 0.001112173483 0.004 15 0.001599257906 0.000159462939 0.003 16 0.000327563874 0.000070846104 0.003 17 0.000140844711 0.000048598099 0.004 18 0.000129745385 0.000053298497 0.003 19 0.000131359468 0.000033718617 0.003 --- complex eigenvalues and eigenvectors 20 0.000124218200 0.000049877412 0.003 21 0.000120970332 0.000028692181 0.003 22 0.000080978063 0.000009481647 0.003 *** CONVERGENCE OF RESIDUAL NORM REACHED *** --- The STEOM iterations have converged --- ------------------ STEOM-CCSD RESULTS ------------------ IROOT= 1: 0.140731 au 3.829 eV 30886.9 cm**-1 Amplitude Excitation -0.112735 11 -> 15 0.909826 13 -> 15 0.367514 13 -> 18 Ground state amplitude: 0.000001 Percentage Active Character 99.79 Amplitude Excitation in Canonical Basis 0.113119 11 -> 15 -0.908983 13 -> 15 -0.354921 13 -> 18 IROOT= 2: 0.261166 au 7.107 eV 57319.4 cm**-1 Amplitude Excitation -0.158317 13 -> 17 0.134916 13 -> 19 0.946524 14 -> 15 0.137774 14 -> 18 Ground state amplitude: 0.031715 Percentage Active Character 99.18 Amplitude Excitation in Canonical Basis -0.175821 13 -> 16 -0.945784 14 -> 15 -0.129256 14 -> 18 IROOT= 3: 0.281558 au 7.662 eV 61794.8 cm**-1 Amplitude Excitation 0.126191 9 -> 15 -0.135403 10 -> 15 0.327452 11 -> 15 0.359829 13 -> 15 -0.843905 13 -> 18 Ground state amplitude: -0.000059 Percentage Active Character 99.27 Amplitude Excitation in Canonical Basis 0.101225 9 -> 15 0.137350 10 -> 15 -0.323823 11 -> 15 -0.352280 13 -> 15 0.840376 13 -> 18 IROOT= 4: 0.319185 au 8.685 eV 70053.1 cm**-1 Amplitude Excitation -0.235106 8 -> 15 -0.255918 8 -> 18 0.883319 10 -> 15 0.211589 10 -> 18 0.133031 11 -> 15 Ground state amplitude: 0.000401 Percentage Active Character 99.04 Amplitude Excitation in Canonical Basis 0.170398 8 -> 15 0.218645 8 -> 18 -0.213691 9 -> 15 -0.122589 9 -> 18 -0.876684 10 -> 15 -0.198197 10 -> 18 -0.139655 11 -> 15 IROOT= 5: 0.359509 au 9.783 eV 78903.1 cm**-1 Amplitude Excitation -0.167564 8 -> 15 0.952708 14 -> 16 -0.188481 14 -> 17 Ground state amplitude: 0.000036 Percentage Active Character 99.15 Amplitude Excitation in Canonical Basis 0.163109 8 -> 15 -0.723603 14 -> 16 -0.642883 14 -> 17 STEOM-CCSD done ( 7.7 sec) Calculating the Dipole integrals ... done Transforming integrals ... done Calculating the Linear Momentum integrals ... done Transforming integrals ... done Calculating angular momentum integrals ... done Transforming integrals ... done -------------------------------------------------------------------- UNRELAXED EXCITED STATE DIPOLE MOMENTS -------------------------------------------------------------------- E(eV) DX(au) DY(au) DZ(au) |D|(D) IROOT= 0: 0.000 0.870454 0.706919 0.000000 2.850243 IROOT= 1: 3.829 0.723929 0.386087 -0.000000 2.085416 IROOT= 2: 7.107 1.186206 1.898032 -0.000067 5.689093 IROOT= 3: 7.662 -0.030834 -1.065995 0.000001 2.710676 IROOT= 4: 8.685 0.657226 0.506477 -0.000232 2.109027 IROOT= 5: 9.783 -0.389909 -1.744239 0.000018 4.542926 -------------------------------------------------------------------- ----------------------------------------------------------------------------- ABSORPTION SPECTRUM VIA TRANSITION ELECTRIC DIPOLE MOMENTS ----------------------------------------------------------------------------- State Energy Wavelength fosc T2 TX TY TZ (cm-1) (nm) (au**2) (au) (au) (au) ----------------------------------------------------------------------------- 1 30886.9 323.8 0.000110089 0.00117 0.00000 0.00000 0.03425 2 57319.4 174.5 0.444765640 2.55450 1.10050 1.15905 0.00002 3 61794.8 161.8 0.000054183 0.00029 0.00017 0.00009 0.01699 4 70053.1 142.7 0.003155733 0.01483 0.00159 0.00126 0.12167 5 78903.1 126.7 0.004242875 0.01770 0.00053 0.00005 0.13305 ------------------------------------------------------------------- CD SPECTRUM ------------------------------------------------------------------- State Energy Wavelength R MX MY MZ (cm-1) (nm) (1e40*cgs) (au) (au) (au) ------------------------------------------------------------------- 1 323.8 30886.9 0.00061 0.33656 0.25499 0.00000 2 174.5 57319.4 -0.00140 -0.00001 -0.00001 -0.05322 3 161.8 61794.8 0.01392 -0.52409 -0.20674 -0.00003 4 142.7 70053.1 -0.01655 -0.12724 0.15726 0.00082 5 126.7 78903.1 -0.01071 -0.21906 0.21141 0.00000 TDM done ( 7.9 sec) STEOM-CCSD done in ( 7.9) ------------------------------------------------------------------------------- TIMINGS ------------------------------------------------------------------------------- Total execution time ... 71.907 sec Localization of occupied MO's ... 0.392 sec ( 0.5%) Fock Matrix Formation ... 0.116 sec ( 0.2%) Global overlap, Fock, MKN matrices ... 0.164 sec ( 0.2%) Differential overlap integrals ... 0.166 sec ( 0.2%) Organizing maps ... 0.002 sec ( 0.0%) RI 3-index integral generations ... 0.452 sec ( 0.6%) RI-PNO integral transformation ... 0.992 sec ( 1.4%) Initial Guess ... 0.110 sec ( 0.2%) DIIS Solver ... 0.139 sec ( 0.2%) State Vector Update ... 0.007 sec ( 0.0%) Sigma-vector construction ... 8.478 sec ( 11.8%) (0-ext) ... 0.904 sec ( 10.7% of sigma) (2-ext Fock) ... 0.003 sec ( 0.0% of sigma) (2-ext) ... 0.789 sec ( 9.3% of sigma) (4-ext) ... 0.495 sec ( 5.8% of sigma) (4-ext-corr) ... 1.414 sec ( 16.7% of sigma) CCSD doubles correction ... 0.192 sec ( 2.3% of sigma) ... 0.607 sec ( 7.2% of sigma) (1-ext) ... 0.064 sec ( 0.8% of sigma) (1-ext) ... 0.002 sec ( 0.0% of sigma) (3-ext) ... 0.039 sec ( 0.5% of sigma) Fock-dressing ... 1.596 sec ( 18.8% of sigma) Singles amplitudes ... 0.302 sec ( 3.6% of sigma) (ik|jl)-dressing ... 0.877 sec ( 10.3% of sigma) (ij|ab),(ia|jb)-dressing ... 1.017 sec ( 12.0% of sigma) Pair energies ... 0.002 sec ( 0.0% of sigma) Total Time for computing EOM-CCSD ... 50.304 sec ( 70.0% of ALL) Dressing integrals ... 0.814 sec ( 1.6% of (EOM)) Initial EOM-Guess ... 0.002 sec ( 0.0% of (EOM)) EOM Singles ... 0.705 sec ( 1.4% of (EOM)) EOM Doubles ... 35.241 sec ( 70.1% of (EOM)) Build Hamiltonian ... 0.229 sec ( 0.5% of (EOM)) Diagonalize Hamiltonian ... 0.106 sec ( 0.2% of (EOM)) Ritz vectors ... 3.236 sec ( 6.4% of (EOM)) Residual vectors ... 3.582 sec ( 7.1% of (EOM)) One-particle density matrix ... 0.057 sec ( 0.1%) Maximum memory used throughout the entire MDCI-calculation: 223.3 MB ------------------------- -------------------- FINAL SINGLE POINT ENERGY -191.081376748163 ------------------------- -------------------- *************************************** * ORCA property calculations * *************************************** --------------------- Active property flags --------------------- (+) Dipole Moment ------------------------------------------------------------------------------ ORCA ELECTRIC PROPERTIES CALCULATION ------------------------------------------------------------------------------ Dipole Moment Calculation ... on Quadrupole Moment Calculation ... off Polarizability Calculation ... off GBWName ... acrolein_DLPNO_STEOM_CCSD.gbw Electron density ... acrolein_DLPNO_STEOM_CCSD.scfp The origin for moment calculation is the CENTER OF MASS = (-0.111583, -0.101447 0.000000) ------------- DIPOLE MOMENT ------------- X Y Z Electronic contribution: -2.18212 -2.16972 -0.00000 Nuclear contribution : 3.34749 3.04341 0.00000 ----------------------------------------- Total Dipole Moment : 1.16537 0.87369 -0.00000 ----------------------------------------- Magnitude (a.u.) : 1.45651 Magnitude (Debye) : 3.70215 -------------------- Rotational spectrum -------------------- Rotational constants in cm-1: 1.599241 0.154449 0.140847 Rotational constants in MHz : 47944.024049 4630.267469 4222.475444 Dipole components along the rotational axes: x,y,z [a.u.] : -1.410331 -0.363852 -0.000000 x,y,z [Debye]: -3.584776 -0.924839 -0.000000 *** MDCI DENSITY *** ------------------------------------------------------------------------------ ORCA ELECTRIC PROPERTIES CALCULATION ------------------------------------------------------------------------------ Dipole Moment Calculation ... on Quadrupole Moment Calculation ... off Polarizability Calculation ... off GBWName ... acrolein_DLPNO_STEOM_CCSD.gbw Electron density ... acrolein_DLPNO_STEOM_CCSD.mdcip The origin for moment calculation is the CENTER OF MASS = (-0.111583, -0.101447 0.000000) ------------- DIPOLE MOMENT ------------- X Y Z Electronic contribution: -2.51932 -2.36212 0.00000 Nuclear contribution : 3.34749 3.04341 0.00000 ----------------------------------------- Total Dipole Moment : 0.82817 0.68129 0.00000 ----------------------------------------- Magnitude (a.u.) : 1.07239 Magnitude (Debye) : 2.72580 -------------------- Rotational spectrum -------------------- Rotational constants in cm-1: 1.599241 0.154449 0.140847 Rotational constants in MHz : 47944.024049 4630.267469 4222.475444 Dipole components along the rotational axes: x,y,z [a.u.] : -1.049408 -0.220828 0.000000 x,y,z [Debye]: -2.667383 -0.561301 0.000000 Timings for individual modules: Sum of individual times ... 76.606 sec (= 1.277 min) GTO integral calculation ... 1.100 sec (= 0.018 min) 1.4 % SCF iterations ... 2.097 sec (= 0.035 min) 2.7 % MDCI module ... 73.409 sec (= 1.223 min) 95.8 % ****ORCA TERMINATED NORMALLY**** TOTAL RUN TIME: 0 days 0 hours 1 minutes 17 seconds 450 msec