Dalton2020.0 { Dalton Program Manual K. Aidas, C. Angeli, K. L. Bak, V. Bakken, R. Bast, L. Boman, B. N. Cabral Tenorio, O. Christiansen, R. Cimiraglia, S. Coriani, J. Cukras, P. Dahle, E. K. Dalskov, T. Enevoldsen, J. J. Eriksen, R. Faber, B. Fern´andez, L. Ferrighi, H. Fliegl, L. Frediani, E. Fromager, B. Gao, A. S. P. Gomes, K. Hald, A. Halkier, F. B. K. Hansen, E. D. Hedeg˚ard, C. H¨attig, H. Heiberg, T. Helgaker, A. C. Hennum, H. Hettema, E. Hjertenæs, D. Hrˇsak, P. A. B. Haase, S. H¨ofener, M. F. Iozzi, C. R. Jacob, B. Jansik, H. J. Aa. Jensen, D. Jonsson, P. Jørgensen, M. Kami´nski,J. Kauczor, S. Kirpekar, E. Kjellgren W. Klopper, S. Knecht, R. Kobayashi, H. Koch, J. Kongsted, A. Ligabue, N. H. List, O. B. Lutnæs, J. I. Melo, K. V. Mikkelsen, R. H. Myhre, C. Neiss, C. B. Nielsen, P. Norman, J. Olsen, J. M. H. Olsen, A. Osted, M. J. Packer, F. Pawlowski, M. N. Pedersen, T. B. Pedersen, P. F. Provasi, P. Reinholdt, Z. Rinkevicius, E. Rudberg, T. A. Ruden, K. Ruud, P. Sa lek, C. C. M. Samson, A. S´anchez de Mer´as,T. Saue, S. P. A. Sauer, B. Schimmelpfennig, K. Sneskov, A. H. Steindal, C. Steinmann, K. O. Sylvester-Hvid, P. R. Taylor, A. M. Teale, D. P. Tew, J. Toulouse, O. Vahtras, L. Visscher, D. J. D. Wilson and H. Agren.˚ Contents Preface x 1 Introduction1 1.1 General description of the manual.......................2 1.2 Acknowledgments.................................3 2 New features in the Dalton releases5 2.1 New features in Dalton2020...........................5 2.2 New features in Dalton2018...........................7 2.3 New features in Dalton2016...........................8 2.4 New features in Dalton2015...........................8 2.5 New features in DALTON2013.........................9 2.6 New features in DALTON2011......................... 10 2.7 New features in Dalton 2.0 (2005)....................... 14 2.8 New features in Dalton 1.2........................... 16 I Dalton Installation Guide 19 3 Installation 20 3.1 Installation instructions............................. 20 3.2 Hardware/software supported.......................... 20 3.3 Source files.................................... 20 4 Maintenance 22 4.1 Memory requirements.............................. 22 4.1.1 Redimensioning Dalton ........................ 22 4.2 New versions, patches.............................. 23 4.3 Reporting bugs and user support........................ 24 i CONTENTS ii II Dalton User's Guide 25 5 Getting started with Dalton 26 5.1 The MOLECULE.INP input file.......................... 26 5.2 The DALTON.INP input file............................ 28 5.2.1 A CASSCF geometry optimization................... 28 5.2.2 A RASSCF calculation of NMR parameters.............. 29 5.2.3 A (parallel) cubic response calculation................. 30 5.2.4 General structure of the DALTON.INP file................ 31 5.3 The POTENTIAL.INP input file.......................... 33 5.4 The first calculation with Dalton ....................... 36 6 Getting the wave function you want 43 6.1 Necessary input to Sirius ............................ 44 6.2 An input example for Sirius .......................... 46 6.3 Hints on the structure of the **WAVE FUNCTIONS input........... 46 6.4 How to restart a wave function calculation.................. 49 6.5 Transfer of molecular orbitals between different computers......... 49 6.6 Wave function input examples......................... 50 7 Potential energy surfaces 59 7.1 Locating stationary points............................ 60 7.1.1 Equilibrium geometries......................... 60 7.1.2 Transition states using the image method............... 65 7.1.3 Transition states using first-order methods............... 67 7.1.4 Transition states following a gradient extremal............ 68 7.1.5 Level-shifted mode-following...................... 70 7.2 Trajectories and Dynamics............................ 71 7.2.1 Intrinsic reaction coordinates...................... 71 7.2.2 Doing a dynamical walk......................... 72 7.2.3 Calculating relative translational energy release............ 75 7.3 Geometry optimization using non-variational wave functions......... 75 8 Molecular vibrations 77 8.1 Vibrational frequencies.............................. 77 8.2 Infrared (IR) intensities............................. 78 8.3 Dipole-gradient based population analysis................... 79 8.4 Raman intensities................................. 80 8.5 Vibrational g factor............................... 82 CONTENTS iii 9 Electric properties 85 9.1 Dipole moment.................................. 85 9.2 Quadrupole moment............................... 85 9.3 Nuclear quadrupole coupling constants..................... 86 9.4 Static and frequency dependent polarizabilities................ 87 10 Calculation of magnetic properties 89 10.1 Magnetizabilities................................. 90 10.2 Nuclear shielding constants........................... 92 10.3 Relativistic corrections to Nuclear shielding constants............ 93 10.4 Rotational g tensor................................ 95 10.5 Nuclear spin{rotation constants......................... 96 10.6 Indirect nuclear spin{spin coupling constants................. 97 10.7 Hyperfine Coupling Tensors........................... 100 10.8 Electronic g-tensors................................ 101 10.9 Zero field splitting................................ 102 10.10CTOCD-DZ calculations............................. 102 10.10.1 General considerations.......................... 103 10.10.2 Input description............................. 104 11 Calculation of optical and Raman properties 107 11.1 Electronic excitation energies and oscillator strengths............. 107 11.2 Vibrational Circular Dichroism calculations.................. 109 11.3 Electronic circular dichroism (ECD)...................... 111 11.4 Optical Rotation................................. 113 11.5 Vibrational Raman Optical Activity (VROA)................. 115 12 Getting the property you want 120 12.1 General considerations.............................. 120 12.2 Input description................................. 121 12.2.1 Linear response.............................. 121 12.2.2 Quadratic response............................ 124 12.2.3 Cubic response.............................. 126 13 Direct and parallel calculations 128 13.1 Direct methods.................................. 128 13.2 Parallel methods................................. 129 CONTENTS iv 14 Finite field calculations 130 14.1 General considerations.............................. 130 14.2 Input description................................. 131 15 Continuum solvation calculations 133 15.1 Polarizable Continuum Model.......................... 133 15.1.1 Input description............................. 133 15.2 Multiconfigurational Self-Consistent Reaction Field.............. 136 15.2.1 General considerations.......................... 136 15.2.2 Input description............................. 138 16 Polarizable embedding calculations 142 16.1 General considerations.............................. 143 16.2 Input description................................. 145 16.2.1 Polarizable density embedding..................... 150 17 Frozen density embedding 157 17.1 General considerations.............................. 157 17.2 Input description................................. 158 18 Vibrational corrections 160 18.1 Effective geometries............................... 160 18.2 Vibrational averaged properties......................... 162 18.3 Vibrationally averaged spin{spin coupling constants............. 164 19 Relativistic Effects 166 20 SOPPA, SOPPA(CC2), SOPPA(CCSD) and RPA(D) 168 20.1 General considerations.............................. 168 20.2 Input description molecular orbital based SOPPA............... 170 20.3 Input description atomic orbital based SOPPA module............ 173 21 NEVPT2 calculations 179 21.1 General considerations.............................. 179 21.2 Input description................................. 180 22 Examples of generalized active space CI calculations 181 22.1 Energy calculation with a GAS-type active space decomposition I...... 181 22.2 Energy calculation with a GAS-type active space decomposition II..... 183 22.3 Energy calculation with a RAS-type active space decomposition....... 184 CONTENTS v 23 Examples of coupled cluster calculations 186 23.1 Multiple model energy calculations....................... 186 23.2 First-order property calculation......................... 187 23.3 Static and frequency-dependent dipole polarizabilities and corresponding dis- persion coefficients................................ 187 23.4 Static and frequency-dependent dipole hyperpolarizabilities and correspond- ing dispersion coefficients............................ 188 23.5 Excitation energies and oscillator strengths.................. 189 23.5.1 Excitation energies (and strengths) of core excited states...... 191 23.6 Gradient calculation, geometry optimization.................. 191 23.7 R12 methods................................... 192 24 Examples of Cholesky decomposition-based calculations 194 24.1 Hartree-Fock energy and polarizability..................... 194 24.2 KT3 magnetic properties using London orbitals................ 195 24.3 MP2 energy.................................... 195 24.4 Restart of MP2 energy.............................. 196 24.5 CC2 magnetic properties using the CTOCD/DZ method........... 198 24.6 Cholesky/CC2 excitation energies........................ 199 24.7 CCSD(T) energy calculation using decomposed energy denominators.... 200 24.8 CCSD excitation energies