***************** * O R C A * ***************** #, ### #### ##### ###### ########, ,,################,,,,, ,,#################################,, ,,##########################################,, ,#########################################, ''#####, ,#############################################,, '####, ,##################################################,,,,####, ,###########'''' ''''############################### ,#####'' ,,,,##########,,,, '''####''' '#### ,##' ,,,,###########################,,, '## ' ,,###'''' '''############,,, ,,##'' '''############,,,, ,,,,,,###'' ,#'' '''#######################''' ' ''''####'''' ,#######, #######, ,#######, ## ,#' '#, ## ## ,#' '#, #''# ,####, ,#, ## ## ## ,#' ## #' '# #' ,# # ## ## ####### ## ,######, #####, # '#, ,#' ## ## '#, ,#' ,# #, #, # # '#######' ## ## '#######' #' '# '####' # # ######################################################### # -***- # # Department of theory and spectroscopy # # # # Frank Neese # # # # Directorship, Architecture, Infrastructure # # SHARK, DRIVERS # # Core code/Algorithms in most modules # # # # Max Planck Institute fuer Kohlenforschung # # Kaiser Wilhelm Platz 1 # # D-45470 Muelheim/Ruhr # # Germany # # # # All rights reserved # # -***- # ######################################################### Program Version 6.1.1 - RELEASE - (GIT: $487d211c$) ($2025-11-21 10:33:24 +0100$) With contributions from (in alphabetic order): [Max-Planck-Institut fuer Kohlenforschung] Daniel Aravena : Magnetic Suceptibility Michael Atanasov : Ab Initio Ligand Field Theory (pilot matlab implementation) Alexander A. Auer : GIAO ZORA, VPT2 properties, NMR spectrum Ute Becker : All parallelization in ORCA, NUMFREQ, NUMCALC Giovanni Bistoni : ED, misc. LED, open-shell LED, HFLD Dmytro Bykov : pre 5.0 version of the SCF Hessian Marcos Casanova-Páez : Triplet and SCS-CIS(D). UHF-(DLPNO)-IP/EA/STEOM-CCSD. UHF-CVS-IP/STEOM-CCSD Vijay G. Chilkuri : MRCI spin determinant printing, contributions to CSF-ICE Pauline Colinet : FMM embedding Dipayan Datta : RHF DLPNO-CCSD density Achintya Kumar Dutta : EOM-CC, STEOM-CC Nicolas Foglia : Exact transition moments, OPA infrastructure, MCD improvements Dmitry Ganyushin : Spin-Orbit,Spin-Spin,Magnetic field MRCI Miquel Garcia-Rates : C-PCM and meta-GGA Hessian, CCSD/C-PCM, Gaussian charge scheme Tiago L. C. Gouveia : GS-ROHF, GS-ROCIS Yang Guo : DLPNO-NEVPT2, F12-NEVPT2, CIM, IAO-localization Andreas Hansen : Spin unrestricted coupled pair/coupled cluster methods Ingolf Harden : AUTO-CI MPn and infrastructure Benjamin Helmich-Paris : MC-RPA, TRAH-(SCF,CASSCF), AVAS, COSX integrals, SCF dyn. polar., MC-PDFT, srDFT Lee Huntington : MR-EOM, pCC Robert Izsak : Overlap fitted RIJCOSX, COSX-SCS-MP3, EOM Riya Kayal : Wick's Theorem for AUTO-CI, AUTO-CI UHF-CCSDT Emily Kempfer : AUTO-CI RHF CISDT and CCSDT, approximate NEVPT4 Christian Kollmar : KDIIS, OOCD, Brueckner-CCSD(T), CCSD density, CASPT2, CASPT2-K, improved NEVPT2 Axel Koslowski : Symmetry handling Simone Kossmann : meta-GGA functionals, TD-DFT gradient, OOMP2, (MP2 Hessian; deprecated post 5.0) Lucas Lang : DCDCAS, Hyperfine gauge corrections, ICE-SOC+SSC Marvin Lechner : AUTO-CI (C++ implementation), FIC-MRCC Spencer Leger : CASSCF response Dagmar Lenk : GEPOL surface, SMD, ORCA-2-JSON Dimitrios Liakos : Extrapolation schemes; Compound Job, Property file Dimitrios Manganas : Further ROCIS development; embedding schemes. LFT, Crystal Embedding Dimitrios Pantazis : SARC Basis sets Anastasios Papadopoulos: AUTO-CI, single reference methods and gradients Taras Petrenko : pre 6.0 DFT Hessian and TD-DFT gradient, ECA, NRVS Petra Pikulova : Analytic Raman intensities Peter Pinski : DLPNO-MP2, DLPNO-MP2 Gradient Shashank Vittal Rao : ES-AILFT, MagRelax Christoph Reimann : Effective Core Potentials Marius Retegan : Local ZFS, SOC Christoph Riplinger : Optimizer, TS searches, QM/MM, DLPNO-CCSD(T), (RO)-DLPNO pert. Triples Michael Roemelt : Original ROCIS implementation, recursive CI coupling coefficients Masaaki Saitow : Open-shell DLPNO-CCSD energy and density Barbara Sandhoefer : DKH picture change effects Yorick L. A. Schmerwitz: GMF and freeze-and-release deltaSCF, NEB S-IDPP initial path Kantharuban Sivalingam : CASSCF convergence/infrastructure, NEVPT2, NEVPT3, NEVPT4(SD), FIC-MRCI and CEPA variants Bernardo de Souza : ESD, SOC TD-DFT Georgi L. Stoychev : AutoAux, RI-MP2 NMR, DLPNO-MP2 response, X2C Van Anh Tran : RI-MP2 g-tensors Willem Van den Heuvel : Paramagnetic NMR Zikuan Wang : NOTCH, Electric field optimization Frank Wennmohs : Technical directorship and infrastructure Hang Xu : AUTO-CI-Response properties [FACCTs GmbH] Markus Bursch, Nicolas Foglia, Miquel Garcia-Rates, Ingolf Harden, Hagen Neugebauer, Anastasios Papadopoulos, Christoph Riplinger, Bernardo de Souza, Georgi L. Stoychev APM, various basis sets, CI-OPT, improved COSX, DLPNO-Multilevel, DOCKER, DRACO, updates on ESD, Fragmentator, GOAT, IRC, LR-CPCM, L-BFGS, MBIS, meta-GGA TD-DFT gradient, ML-optimized integration grids, MM, NACMEs, nearIR, NEB, NEB-TS, NL-DFT gradient (VV10), 2- and 3-layer-ONIOM, interface openCOSMO-RS, QMMM, Crystal-QMMM, RESP, rigid body optimization, SF, symmetry and pop. for TD-DFT, various functionals, SOLVATOR [Other institutions] V. Asgeirsson : NEB Christoph Bannwarth : sTDA-DFT, sTD-DFT, PBEh-3c, B97-3c, D3 Giovanni Bistoni : ETS/NOCV, ADLD/ADEX, COVALED Martin Brehm : Molecular dynamics Ronald Cardenas : ETS/NOCV Martina Colucci : COVALED Sebastian Ehlert : rSCAN, r2SCAN, r2SCAN-3c, D4, dhf basis sets Marvin Friede : D4 for Fr, Ra, Ac-Lr Lars Goerigk : TD-DFT with DH, B97 family of functionals Stefan Grimme : VdW corrections, initial TS optimization, DFT functionals, gCP, sTDA/sTD-DF Waldemar Hujo : DFT-NL H. Jonsson : NEB Holger Kruse : gCP Marcel Mueller : wB97X-3c, vDZP basis set Hagen Neugebauer : wr2SCAN, Native XTB Gianluca Regni : ADLD/ADEX Tobias Risthaus : pre 6.0 range-separated hybrid DFT and stability analysis Lukas Wittmann : regularized MP2, r2SCAN double-hybrids, wr2SCAN We gratefully acknowledge several colleagues who have allowed us to interface, adapt or use parts of their codes: Ed Valeev, F. Pavosevic, A. Kumar : LibInt (2-el integral package), F12 methods Garnet Chan, S. Sharma, J. Yang, R. Olivares : DMRG Ulf Ekstrom : XCFun DFT Library Mihaly Kallay : mrcc (arbitrary order and MRCC methods) Frank Weinhold : gennbo (NPA and NBO analysis) Simon Mueller : openCOSMO-RS Christopher J. Cramer and Donald G. Truhlar : smd solvation model S Lehtola, MJT Oliveira, MAL Marques : LibXC Library Liviu Ungur et al : ANISO software Your calculation uses the libint2 library for the computation of 2-el integrals For citations please refer to: http://libint.valeyev.net Your ORCA version has been built with support for libXC version: 7.0.0 For citations please refer to: https://libxc.gitlab.io This ORCA versions uses: CBLAS interface : Fast vector & matrix operations LAPACKE interface : Fast linear algebra routines SCALAPACK package : Parallel linear algebra routines Shared memory : Shared parallel matrices BLAS/LAPACK : OpenBLAS 0.3.29 USE64BITINT DYNAMIC_ARCH NO_AFFINITY Haswell SINGLE_THREADED Core in use : Haswell Copyright (c) 2011-2014, The OpenBLAS Project *********************************** * Starting time: Tue Jul 14 14:11:41 2026 * Host name: kseng-Akoya-P5320-E-MD8875-2431 * Process ID: 74333 * Working dir.: /home/kseng/Masterthesis/nmr-project/Vanilla/3,4-Dihydroxybenzaldehyd *********************************** *************************************** The coordinates will be read from file: orca.xyz *************************************** Your calculation utilizes the atom-pairwise dispersion correction based on EEQ partial charges (D4) Warning: RI is on but no J-basis has been assigned. Assigning Def2/J (nothing to worry about!) ================================================================================ ----- Orbital basis set information ----- Your calculation utilizes the basis: def2-SVP F. Weigend and R. Ahlrichs, Phys. Chem. Chem. Phys. 7, 3297 (2005). ----- AuxJ basis set information ----- Your calculation utilizes the auxiliary basis: def2/J H-Rn: F. Weigend, Phys. Chem. Chem. Phys. 8, 1057 (2006). Fr-Lr: K. Eichkorn, F. Weigend, O. Treutler, R. Ahlrichs; Theor. Chem. Acc. 97, 119 (1997). ================================================================================ WARNINGS Please study these warnings very carefully! ================================================================================ WARNING: Geometry Optimization ===> : Switching off AutoStart For restart on a previous wavefunction, please use MOREAD ================================================================================ INPUT FILE ================================================================================ NAME = orca.inp | 1> !PBE D4 DEF2-SVP OPT | 2> | 3> %PAL NPROCS 4 END | 4> | 5> * xyzfile 0 1 orca.xyz | 6> | 7> ****END OF INPUT**** ================================================================================ ***************************** * Geometry Optimization Run * ***************************** Geometry optimization settings: Update method Update .... BFGS Choice of coordinates CoordSys .... (2022) Redundant Internals Initial Hessian InHess .... Almloef's Model Max. no of cycles MaxIter .... 50 Convergence Tolerances: Energy Change TolE .... 5.0000e-06 Eh Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr Max. Displacement TolMAXD .... 4.0000e-03 bohr RMS Displacement TolRMSD .... 2.0000e-03 bohr Strict Convergence .... False ------------------------------------------------------------------------------ ORCA OPTIMIZATION COORDINATE SETUP ------------------------------------------------------------------------------ The optimization will be done in redundant internal coordinates (2022) Making redundant internal coordinates ... (2022 redundants) done Evaluating the initial hessian ... (Almloef) done Evaluating the coordinates ... done Calculating the B-matrix .... done Calculating the G-matrix .... done The number of degrees of freedom .... 71 ----------------------------------------------------------------- Redundant Internal Coordinates ----------------------------------------------------------------- Definition Initial Value Approx d2E/dq ----------------------------------------------------------------- 1. B(C 1,O 0) 1.3979 0.543598 2. B(C 2,C 1) 1.3819 0.643598 3. B(C 3,C 2) 1.3793 0.649902 4. B(C 4,C 3) 1.4006 0.600859 5. B(C 5,C 4) 1.4768 0.454205 6. B(O 6,C 5) 1.2739 0.857295 7. B(C 7,C 4) 1.3811 0.645465 8. B(C 8,C 7) 1.3975 0.607744 9. B(C 8,C 1) 1.3875 0.630506 10. B(O 9,C 8) 1.3922 0.555181 11. B(H 10,O 0) 1.0222 0.413732 12. B(H 11,C 2) 1.0973 0.350570 13. B(H 12,C 3) 1.0906 0.359367 14. B(H 13,C 5) 1.0825 0.370149 15. B(H 14,C 7) 1.0840 0.368071 16. B(H 15,O 9) 1.0193 0.418176 17. A(C 1,O 0,H 10) 121.2221 0.348117 18. A(O 0,C 1,C 2) 122.4363 0.424011 19. A(C 2,C 1,C 8) 118.0146 0.438322 20. A(O 0,C 1,C 8) 119.5491 0.422456 21. A(C 1,C 2,C 3) 122.4328 0.440726 22. A(C 3,C 2,H 11) 119.3138 0.354123 23. A(C 1,C 2,H 11) 118.2534 0.353539 24. A(C 2,C 3,C 4) 118.5529 0.435298 25. A(C 4,C 3,H 12) 120.9771 0.350922 26. A(C 2,C 3,H 12) 120.4699 0.355614 27. A(C 5,C 4,C 7) 119.3720 0.413542 28. A(C 3,C 4,C 7) 120.5780 0.434761 29. A(C 3,C 4,C 5) 120.0501 0.408325 30. A(O 6,C 5,H 13) 122.4478 0.372417 31. A(C 4,C 5,O 6) 119.3388 0.432227 32. A(C 4,C 5,H 13) 118.2134 0.336498 33. A(C 8,C 7,H 14) 121.8777 0.353024 34. A(C 4,C 7,H 14) 118.9912 0.356647 35. A(C 4,C 7,C 8) 119.1311 0.435654 36. A(C 7,C 8,O 9) 118.3742 0.421274 37. A(C 1,C 8,O 9) 120.3352 0.424051 38. A(C 1,C 8,C 7) 121.2906 0.433819 39. A(C 8,O 9,H 15) 116.2110 0.349987 40. D(C 2,C 1,O 0,H 10) 110.9862 0.021350 41. D(C 8,C 1,O 0,H 10) -69.0135 0.021350 42. D(H 11,C 2,C 1,C 8) -179.9998 0.028801 43. D(C 3,C 2,C 1,O 0) -179.9996 0.028801 44. D(H 11,C 2,C 1,O 0) 0.0005 0.028801 45. D(C 3,C 2,C 1,C 8) 0.0001 0.028801 46. D(C 4,C 3,C 2,C 1) -0.0002 0.029408 47. D(H 12,C 3,C 2,H 11) -0.0003 0.029408 48. D(C 4,C 3,C 2,H 11) 179.9997 0.029408 49. D(H 12,C 3,C 2,C 1) 179.9998 0.029408 50. D(C 7,C 4,C 3,C 2) 0.0001 0.024893 51. D(C 5,C 4,C 3,H 12) 0.0003 0.024893 52. D(C 7,C 4,C 3,H 12) -179.9998 0.024893 53. D(C 5,C 4,C 3,C 2) -179.9998 0.024893 54. D(H 13,C 5,C 4,C 7) 179.9990 0.014058 55. D(H 13,C 5,C 4,C 3) -0.0011 0.014058 56. D(O 6,C 5,C 4,C 7) -0.0010 0.014058 57. D(O 6,C 5,C 4,C 3) 179.9989 0.014058 58. D(H 14,C 7,C 4,C 5) 0.0002 0.028980 59. D(H 14,C 7,C 4,C 3) -179.9997 0.028980 60. D(C 8,C 7,C 4,C 5) 179.9999 0.028980 61. D(C 8,C 7,C 4,C 3) -0.0000 0.028980 62. D(O 9,C 8,C 7,H 14) -0.0002 0.025498 63. D(O 9,C 8,C 7,C 4) -179.9999 0.025498 64. D(C 1,C 8,C 7,H 14) 179.9996 0.025498 65. D(C 1,C 8,C 7,C 4) -0.0001 0.025498 66. D(O 9,C 8,C 1,C 2) 179.9999 0.027566 67. D(O 9,C 8,C 1,O 0) -0.0004 0.027566 68. D(C 7,C 8,C 1,C 2) 0.0000 0.027566 69. D(C 7,C 8,C 1,O 0) 179.9997 0.027566 70. D(H 15,O 9,C 8,C 1) 110.1326 0.022312 71. D(H 15,O 9,C 8,C 7) -69.8676 0.022312 ----------------------------------------------------------------- Number of atoms .... 16 Number of degrees of freedom .... 71 ************************************************************* * GEOMETRY OPTIMIZATION CYCLE 1 * ************************************************************* --------------------------------- CARTESIAN COORDINATES (ANGSTROEM) --------------------------------- O -2.910521 -0.398302 -0.222661 C -1.515776 -0.342989 -0.146898 C -0.739792 -1.466805 0.064326 C 0.636372 -1.412144 0.139075 C 1.265810 -0.169243 -0.005078 C 2.737569 -0.072590 0.069265 O 3.295908 1.064668 -0.063716 C 0.521664 0.974759 -0.217344 C -0.870747 0.877494 -0.286829 O -1.605308 2.040474 -0.501300 H -3.497447 0.008311 0.508838 H -1.245858 -2.434069 0.175530 H 1.217554 -2.319543 0.306898 H 3.302301 -0.980895 0.236245 H 1.035396 1.923210 -0.325342 H -1.627126 2.707665 0.268992 ---------------------------- CARTESIAN COORDINATES (A.U.) ---------------------------- NO LB ZA FRAG MASS X Y Z 0 O 8.0000 0 15.999 -5.500088 -0.752682 -0.420768 1 C 6.0000 0 12.011 -2.864402 -0.648155 -0.277597 2 C 6.0000 0 12.011 -1.398004 -2.771860 0.121559 3 C 6.0000 0 12.011 1.202569 -2.668565 0.262814 4 C 6.0000 0 12.011 2.392034 -0.319823 -0.009596 5 C 6.0000 0 12.011 5.173256 -0.137175 0.130892 6 O 8.0000 0 15.999 6.228363 2.011931 -0.120406 7 C 6.0000 0 12.011 0.985802 1.842028 -0.410721 8 C 6.0000 0 12.011 -1.645473 1.658223 -0.542028 9 O 8.0000 0 15.999 -3.033592 3.855937 -0.947320 10 H 1.0000 0 1.008 -6.609217 0.015706 0.961564 11 H 1.0000 0 1.008 -2.354330 -4.599724 0.331704 12 H 1.0000 0 1.008 2.300844 -4.383301 0.579953 13 H 1.0000 0 1.008 6.240445 -1.853623 0.446438 14 H 1.0000 0 1.008 1.956615 3.634340 -0.614807 15 H 1.0000 0 1.008 -3.074823 5.116745 0.508321 -------------------------------- INTERNAL COORDINATES (ANGSTROEM) -------------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 C 1 0 0 1.397895981525 0.00000000 0.00000000 C 2 1 0 1.381929501924 122.43634027 0.00000000 C 3 2 1 1.379276111886 122.43282537 180.00037706 C 4 3 2 1.400633849032 118.55294794 0.00000000 C 5 4 3 1.476801692218 120.05007434 180.00023801 O 6 5 4 1.273884666619 119.33879537 179.99885873 C 5 4 3 1.381141086231 120.57795895 0.00000000 C 2 1 3 1.387523639039 119.54910475 180.00029236 O 9 2 1 1.392156655324 120.33519891 0.00000000 H 1 2 3 1.022206949813 121.22210827 110.98624209 H 3 2 1 1.097300675142 118.25336093 0.00000000 H 4 3 2 1.090554914552 120.46993472 179.99980482 H 6 5 4 1.082507517410 118.21342175 0.00000000 H 8 5 4 1.084040329152 118.99122508 180.00027963 H 10 9 2 1.019298592596 116.21098261 110.13256367 --------------------------- INTERNAL COORDINATES (A.U.) --------------------------- O 0 0 0 0.000000000000 0.00000000 0.00000000 C 1 0 0 2.641640568791 0.00000000 0.00000000 C 2 1 0 2.611468295023 122.43634027 0.00000000 C 3 2 1 2.606454114523 122.43282537 180.00037706 C 4 3 2 2.646814388570 118.55294794 0.00000000 C 5 4 3 2.790750752404 120.05007434 180.00023801 O 6 5 4 2.407293146111 119.33879537 179.99885873 C 5 4 3 2.609978405284 120.57795895 0.00000000 C 2 1 3 2.622039682125 119.54910475 180.00029236 O 9 2 1 2.630794814078 120.33519891 0.00000000 H 1 2 3 1.931691187338 121.22210827 110.98624209 H 3 2 1 2.073597762586 118.25336093 0.00000000 H 4 3 2 2.060850122506 120.46993472 179.99980482 H 6 5 4 2.045642745816 118.21342175 0.00000000 H 8 5 4 2.048539340224 118.99122508 180.00027963 H 10 9 2 1.926195188699 116.21098261 110.13256367 --------------------- BASIS SET INFORMATION --------------------- There are 3 groups of distinct atoms Group 1 Type O : 7s4p1d contracted to 3s2p1d pattern {511/31/1} Group 2 Type C : 7s4p1d contracted to 3s2p1d pattern {511/31/1} Group 3 Type H : 4s1p contracted to 2s1p pattern {31/1} Atom 0O basis set group => 1 Atom 1C basis set group => 2 Atom 2C basis set group => 2 Atom 3C basis set group => 2 Atom 4C basis set group => 2 Atom 5C basis set group => 2 Atom 6O basis set group => 1 Atom 7C basis set group => 2 Atom 8C basis set group => 2 Atom 9O basis set group => 1 Atom 10H basis set group => 3 Atom 11H basis set group => 3 Atom 12H basis set group => 3 Atom 13H basis set group => 3 Atom 14H basis set group => 3 Atom 15H basis set group => 3 --------------------------------- AUXILIARY/J BASIS SET INFORMATION --------------------------------- There are 3 groups of distinct atoms Group 1 Type O : 12s5p4d2f1g contracted to 6s4p3d1f1g pattern {711111/2111/211/2/1} Group 2 Type C : 12s5p4d2f1g contracted to 6s4p3d1f1g pattern {711111/2111/211/2/1} Group 3 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} Atom 0O basis set group => 1 Atom 1C basis set group => 2 Atom 2C basis set group => 2 Atom 3C basis set group => 2 Atom 4C basis set group => 2 Atom 5C basis set group => 2 Atom 6O basis set group => 1 Atom 7C basis set group => 2 Atom 8C basis set group => 2 Atom 9O basis set group => 1 Atom 10H basis set group => 3 Atom 11H basis set group => 3 Atom 12H basis set group => 3 Atom 13H basis set group => 3 Atom 14H basis set group => 3 Atom 15H basis set group => 3 ORCA finished by error termination in Startup Calling Command: mpirun -np 4 /home/kseng/orca_6_1_1/orca_startup_mpi orca.int.tmp orca [file orca_tools/qcmsg.cpp, line 394]: .... aborting the run