DALTON Release 2 Program Manual C. Angeli, K. L. Bak, V. Bakken, O. Christiansen, R. Cimiraglia, S. Coriani, P. Dahle, E. K. Dalskov, T. Enevoldsen, B. Fernandez, C. H¨attig, K. Hald, A. Halkier, H. Heiberg, T. Helgaker, H. Hettema, H. J. Aa. Jensen, D. Jonsson, P. Jørgensen, S. Kirpekar, W. Klopper, R. Kobayashi, H. Koch, A. Ligabue, O. B. Lutnæs, K. V. Mikkelsen, P. Norman, J. Olsen, M. J. Packer, T. B. Pedersen, Z. Rinkevicius, E. Rudberg, T. A. Ruden, K. Ruud, P. Sa lek, A. Sanchez de Meras, T. Saue, S. P. A. Sauer, B. Schimmelpfennig, K. O. Sylvester-Hvid, P. R. Taylor, O. Vahtras, D. J. Wilson, and H. Agren,˚ Contents Preface viii 1 Introduction 1 1.1 General description of the manual . .... 2 1.2 Acknowledgments................................. 3 2 New features in Dalton 4 2.1 NewfeaturesinDalton2.0 .. .. .. .. .. .. .. .. 4 2.2 NewfeaturesinDalton1.2 .. .. .. .. .. .. .. .. 7 I DALTON Installation Guide 10 3 Installation 11 3.1 Hardware/softwaresupported . 11 3.2 Sourcefiles .................................... 11 3.3 Installing the program using the Makefile . ...... 12 3.4 Running the dalton testsuite ......................... 15 4 Maintenance 16 4.1 Memoryrequirements .............................. 16 4.1.1 Redimensioning dalton ......................... 16 4.2 Newversions,patches ............................. 17 4.3 Reportingbugsandusersupport . 18 II DALTON User’s Guide 19 5 Getting started with dalton 20 5.1 TheDALTON.INPfile.............................. 20 5.1.1 A CASSCF geometry optimization . 20 i CONTENTS ii 5.1.2 A RASSCF calculation of NMR parameters . 21 5.1.3 A parallel cubic response calculation . ..... 22 5.2 General structure of the DALTON.INP file . 23 5.3 The molecule inputfile ............................ 25 5.4 The first calculation with dalton ....................... 27 6 Getting the wave function you want 31 6.1 NecessaryinputtoSIRIUS . 32 6.2 AninputexampleforSIRIUS . 32 6.3 Hints on the structure of the input for the **WAVE FUNCTIONS inputmodule........................ 34 6.4 How to restart a wave function calculation . ...... 36 6.5 Transfer of molecular orbitals between different computers ......... 37 6.6 Wavefunctioninputexamples . 37 7 Potential energy surfaces 46 7.1 Locatingstationarypoints. 47 7.1.1 Equilibriumgeometries . 47 7.1.2 Transition states using the image method . 52 7.1.3 Transition states using first-order methods . ....... 54 7.1.4 Transition states following a gradient extremal . ........ 55 7.1.5 Level-shifted mode-following . 57 7.2 TrajectoriesandDynamics. 58 7.2.1 Intrinsic reaction coordinates . 58 7.2.2 Doingadynamicalwalk . .. .. .. .. .. .. .. 59 7.2.3 Calculating relative translational energy release . ........... 62 7.3 Geometry optimization using non-variational wave functions......... 62 8 Molecular vibrations 64 8.1 Vibrationalfrequencies. 64 8.2 Infrared(IR)intensities . 65 8.3 Dipole-gradient based population analysis . ......... 66 8.4 Ramanintensities................................ 67 9 Electric properties 70 9.1 Dipolemoment .................................. 70 9.2 Quadrupolemoment ............................... 70 9.3 Nuclear quadrupole coupling constants . ....... 71 9.4 Static and frequency dependent polarizabilities . ........... 72 CONTENTS iii 10 Calculation of magnetic properties 74 10.1 Magnetizabilities . 75 10.2 Nuclear shielding constants . ..... 77 10.3 Rotational g tensor................................ 78 10.4 Nuclear spin–rotation constants . ....... 79 10.5 Indirect nuclear spin–spin coupling constants . ........... 80 10.6 HyperfineCouplingTensors . 82 10.7 Electronicg-tensors. 83 10.8 Zerofieldsplitting .............................. 84 10.9 CTOCD-DZcalculations. 84 10.9.1 General considerations . 85 10.9.2 Inputdescription . 86 11 Calculation of optical and Raman properties 89 11.1 Vibrational Circular Dichroism calculations . ........... 89 11.2 Electronic circular dichroism (ECD) and electronic absorption calculations . 91 11.3 OpticalRotation ................................ 93 11.4 Vibrational Raman Optical Activity (VROA) . ....... 95 12 Getting the property you want 99 12.1 Generalconsiderations . 99 12.2 Inputdescription ............................... 100 12.2.1 Linearresponse.............................. 100 12.2.2 Quadraticresponse. 102 12.2.3 Cubicresponse .............................. 104 13 Direct and parallel calculations 106 13.1Directmethods .................................. 106 13.2 Parallelmethods ................................ 107 14 Finite field calculations 108 14.1 Generalconsiderations . 108 14.2 Inputdescription ............................... 109 15 Solvent calculations 111 15.1 Generalconsiderations . 111 15.2 Inputdescription ............................... 112 15.2.1 Geometry optimization . 114 15.2.2 Non-equilibrium solvation . 114 CONTENTS iv 16 Vibrational corrections 117 16.1 Effectivegeometries .. .. .. .. .. .. .. .. 117 16.2 Vibrational averaged properties . ....... 119 16.3 Vibrationally averaged spin–spin coupling constants ............. 121 17 Relativistic Effects 123 18 SOPPA and SOPPA(CCSD) calculations 125 18.1 Generalconsiderations . 125 18.2 Inputdescription ............................... 126 19 NEVPT2 calculations 129 19.1 Generalconsiderations . 129 19.2 Inputdescription ............................... 130 20 Examples of coupled cluster calculations 131 20.1 Multiple model energy calculations . ....... 131 20.2 First-order property calculation . ........ 132 20.3 Static and frequency-dependent dipole polarizabilities and corresponding dis- persioncoefficients ................................ 132 20.4 Static and frequency-dependent dipole hyperpolarizabilities and correspond- ingdispersioncoefficients . 133 20.5 Excitation energies and oscillator strengths . ........... 134 20.6 Gradient calculation, geometry optimization . ........... 135 20.7R12methods ................................... 136 III DALTON Reference Manual 137 21 General input module 138 21.1 General input to DALTON : **DALTON ..................... 138 21.1.1 General: *OPTIMIZE ........................... 141 21.1.2 Parallel calculations : *PARALLEL .................... 150 21.1.3 Geometry optimization: *WALK ..................... 151 21.2 Numerical differentiation : **NMDDRV ...................... 156 21.2.1 Vibrational averaging of molecular properties: *PROPAV ....... 159 21.2.2 Vibrational analysis: *VIBANA ...................... 160 CONTENTS v 22 Integral evaluation, hermit 161 22.1General ...................................... 161 22.2 **INTEGRALS directives ............................. 162 22.2.1 End of input: *END OF .......................... 162 22.2.2 General: **INTEGRALS .......................... 162 22.2.3 One-electron integrals: *ONEINT ..................... 179 22.2.4 General: *READIN ............................ 180 22.2.5 Integral sorting: *SORINT ........................ 181 22.2.6 Construction of the supermatrix file: *SUPINT ............. 181 22.2.7 Two-electron integrals using twoint: *TWOINT ............ 182 22.2.8 Two-electron integrals using eri: *ER2INT ............... 183 23 molecule input style 186 23.1 General molecule input ............................ 187 23.2 Cartesiangeometryinput . 190 23.3Z-matrixinput .................................. 193 23.4 Usingbasissetlibraries . 194 23.5 Auxiliarybasissets. 197 23.6 The basis sets supplied with dalton ...................... 198 24 Molecular wave functions, sirius 202 24.1 General notes for the sirius inputreferencemanual . 202 24.2 Main input groups in the **WAVE FUNCTIONS input module . 203 24.2.1 **WAVE FUNCTIONS ............................ 204 24.2.2 *AUXILIARY INPUT ............................ 206 24.2.3 *CI INPUT ................................ 206 24.2.4 *CI VECTOR ................................ 207 24.2.5 *CONFIGURATION INPUT ......................... 208 24.2.6 *DFT INPUT ................................ 209 24.2.7 DFTfunctionals ............................. 210 24.2.8 *HAMILTONIAN .............................. 213 24.2.9 *MP2 INPUT ................................ 213 24.2.10 *NEVPT2 INPUT .............................. 214 24.2.11 *OPTIMIZATION .............................. 215 24.2.12 *ORBITAL INPUT ............................. 219 24.2.13 *POPULATION ANALYSIS ......................... 223 24.2.14 *PRINT LEVELS .............................. 224 24.2.15 *SCF INPUT ................................ 225 24.2.16 *SOLVENT ................................. 229 CONTENTS vi 24.2.17 *STEP CONTROL .............................. 230 24.2.18 *TRANSFORMATION ............................ 232 24.3 **MOLORB inputmodule............................. 233 25 HF, SOPPA, and MCSCF molecular properties, ABACUS 234 25.1 Directives for evaluation of HF, SOPPA, and MCSCF molecular properties 234 25.1.1 General: **PROPERTIES ......................... 234 25.1.2 Calculation of Atomic Axial Tensors (AATs): *AAT .......... 242 25.1.3 Linear response calculation: *ABALNR .................. 243 25.1.4 Dipole moment and dipole gradient contributions: *DIPCTL . 244 25.1.5 End of input: *END OF .......................... 245 25.1.6 Calculation of excitation energies: *EXCITA .............. 245 25.1.7 One-electron expectation values: *EXPECT ............... 247 25.1.8 Geometry analysis: *GEOANA ...................... 248 25.1.9 Right-hand sides for response equations: *GETSGY .......... 249 25.1.10 Linear response calculation: *LINRES .................. 253 25.1.11 Nuclear contributions: *NUCREP ..................... 254 25.1.12 One-electron integrals: *ONEINT ....................