Dalton2015 { Dalton Program Manual K. Aidas C. Angeli, K. L. Bak, V. Bakken, R. Bast, L. Boman, O. Christiansen, R. Cimiraglia, S. Coriani, J. Cukras, P. Dahle, E. K. Dalskov, T. Enevoldsen, J. J. Eriksen, B. Fern´andez,L. Ferrighi, H. Fliegl, L. Frediani, B. Gao, K. Hald, A. Halkier, E. D. Hedeg˚ard, C. H¨attig,H. Heiberg, T. Helgaker, A. C. Hennum, H. Hettema, E. Hjertenæs, M. F. Iozzi, B. Jansik, H. J. Aa. Jensen, D. Jonsson, P. Jørgensen, M. Kami´nski, J. Kauczor, S. Kirpekar, 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, 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, O. Vahtras, D. J. D. Wilson and H. Agren.˚ Contents Preface ix 1 Introduction1 1.1 General description of the manual.......................2 1.2 Acknowledgments.................................3 I Dalton Installation Guide4 2 Installation5 2.1 Installation instructions.............................5 2.2 Hardware/software supported..........................5 2.3 Source files....................................5 3 Maintenance7 3.1 Memory requirements..............................7 3.1.1 Redimensioning Dalton ........................7 3.2 New versions, patches..............................8 3.3 Reporting bugs and user support........................9 II Dalton User's Guide 10 4 Getting started with Dalton 11 4.1 The MOLECULE.INP input file.......................... 11 4.2 The DALTON.INP input file............................ 13 4.2.1 A CASSCF geometry optimization................... 13 4.2.2 A RASSCF calculation of NMR parameters.............. 14 4.2.3 A (parallel) cubic response calculation................. 15 4.2.4 General structure of the DALTON.INP file................ 16 i CONTENTS ii 4.3 The POTENTIAL.INP input file.......................... 18 4.4 The first calculation with Dalton ....................... 21 5 Getting the wave function you want 27 5.1 Necessary input to Sirius ............................ 28 5.2 An input example for Sirius .......................... 28 5.3 Hints on the structure of the **WAVE FUNCTIONS input........... 30 5.4 How to restart a wave function calculation.................. 32 5.5 Transfer of molecular orbitals between different computers......... 33 5.6 Wave function input examples......................... 33 6 Potential energy surfaces 42 6.1 Locating stationary points............................ 43 6.1.1 Equilibrium geometries......................... 43 6.1.2 Transition states using the image method............... 48 6.1.3 Transition states using first-order methods............... 50 6.1.4 Transition states following a gradient extremal............ 51 6.1.5 Level-shifted mode-following...................... 53 6.2 Trajectories and Dynamics............................ 54 6.2.1 Intrinsic reaction coordinates...................... 54 6.2.2 Doing a dynamical walk......................... 55 6.2.3 Calculating relative translational energy release............ 58 6.3 Geometry optimization using non-variational wave functions......... 58 7 Molecular vibrations 60 7.1 Vibrational frequencies.............................. 60 7.2 Infrared (IR) intensities............................. 61 7.3 Dipole-gradient based population analysis................... 62 7.4 Raman intensities................................. 63 7.5 Vibrational g factor............................... 65 8 Electric properties 68 8.1 Dipole moment.................................. 68 8.2 Quadrupole moment............................... 68 8.3 Nuclear quadrupole coupling constants..................... 69 8.4 Static and frequency dependent polarizabilities................ 70 9 Calculation of magnetic properties 72 9.1 Magnetizabilities................................. 73 9.2 Nuclear shielding constants........................... 75 CONTENTS iii 9.3 Relativistic corrections to Nuclear shielding constants............ 76 9.4 Rotational g tensor................................ 78 9.5 Nuclear spin{rotation constants......................... 79 9.6 Indirect nuclear spin{spin coupling constants................. 80 9.7 Hyperfine Coupling Tensors........................... 83 9.8 Electronic g-tensors................................ 84 9.9 Zero field splitting................................ 85 9.10 CTOCD-DZ calculations............................. 85 9.10.1 General considerations.......................... 86 9.10.2 Input description............................. 87 10 Calculation of optical and Raman properties 90 10.1 Electronic excitation energies and oscillator strengths............. 90 10.2 Vibrational Circular Dichroism calculations.................. 92 10.3 Electronic circular dichroism (ECD)...................... 94 10.4 Optical Rotation................................. 96 10.5 Vibrational Raman Optical Activity (VROA)................. 98 11 Getting the property you want 103 11.1 General considerations.............................. 103 11.2 Input description................................. 104 11.2.1 Linear response.............................. 104 11.2.2 Quadratic response............................ 107 11.2.3 Cubic response.............................. 109 12 Direct and parallel calculations 111 12.1 Direct methods.................................. 111 12.2 Parallel methods................................. 112 13 Finite field calculations 113 13.1 General considerations.............................. 113 13.2 Input description................................. 114 14 Continuum solvation calculations 116 14.1 Polarizable Continuum Model.......................... 116 14.1.1 Input description............................. 116 14.2 Multiconfigurational Self-Consistent Reaction Field.............. 119 14.2.1 General considerations.......................... 119 14.2.2 Input description............................. 121 CONTENTS iv 15 Polarizable embedding calculations 125 15.1 General considerations.............................. 126 15.2 Input description................................. 127 16 Vibrational corrections 134 16.1 Effective geometries............................... 134 16.2 Vibrational averaged properties......................... 136 16.3 Vibrationally averaged spin{spin coupling constants............. 138 17 Relativistic Effects 140 18 SOPPA, SOPPA(CC2), SOPPA(CCSD) and RPA(D) 142 18.1 General considerations.............................. 142 18.2 Input description molecular orbital based SOPPA............... 144 18.3 Input description atomic orbital based SOPPA module............ 147 19 NEVPT2 calculations 151 19.1 General considerations.............................. 151 19.2 Input description................................. 152 20 Examples of generalized active space CI calculations 153 20.1 Energy calculation with a GAS-type active space decomposition I...... 153 20.2 Energy calculation with a GAS-type active space decomposition II..... 155 20.3 Energy calculation with a RAS-type active space decomposition....... 156 21 Examples of coupled cluster calculations 158 21.1 Multiple model energy calculations....................... 158 21.2 First-order property calculation......................... 159 21.3 Static and frequency-dependent dipole polarizabilities and corresponding dis- persion coefficients................................ 159 21.4 Static and frequency-dependent dipole hyperpolarizabilities and correspond- ing dispersion coefficients............................ 160 21.5 Excitation energies and oscillator strengths.................. 161 21.6 Gradient calculation, geometry optimization.................. 162 21.7 R12 methods................................... 163 22 Examples of Cholesky decomposition-based calculations 164 22.1 Hartree-Fock energy and polarizability..................... 164 22.2 KT3 magnetic properties using London orbitals................ 165 22.3 MP2 energy.................................... 165 CONTENTS v 22.4 Restart of MP2 energy.............................. 166 22.5 CC2 magnetic properties using the CTOCD/DZ method........... 168 22.6 Cholesky/CC2 excitation energies........................ 169 22.7 CCSD(T) energy calculation using decomposed energy denominators.... 170 22.8 CCSD excitation energies using a reduced active subsystem......... 171 23 Aspects of symmetry in Dalton 173 23.1 Specifying symmetry by generators....................... 173 23.2 Labelling of irreducible representations..................... 177 23.3 Nuclear coordinates; symmetry-lowering.................... 177 23.4 Treatment of higher symmetries......................... 178 III Dalton Reference Manual 182 24 General input module 183 24.1 General input to DALTON : **DALTON ..................... 183 24.1.1 Geometry optimization module 1: *OPTIMIZE ............. 187 24.1.2 Parallel calculations : *PARALLEL .................... 196 24.1.3 Polarizable embedding model: *PEQM .................. 197 24.1.4 QM/MM model: *QM3 .......................... 200 24.1.5 Polarizable continuum model: *PCM .................. 200 24.1.6 The PCM cavity: *PCMCAV ....................... 202 24.1.7 Potential derived charges: *QFIT .................... 203 24.1.8 Geometry optimization module 2: *WALK ................ 204 24.1.9 Molecule geometry and basis sets, *MOLBAS