SCM: ADF Manual
ADF ManualADF Program System
Release 2014
Scientific Computing & Modelling NVVrije Universiteit, Theoretical ChemistryDe Boelelaan 1083; 1081 HV Amsterdam; The NetherlandsWWW: www.scm.comE-mail: [email protected]
Copyright 1993-2014: SCM / Vrije Universiteit, Theoretical Chemistry, Amsterdam, The NetherlandsAll rights reserved
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Table of ContentsADF Manual..................................................................................................................................................... 1Table of Contents ........................................................................................................................................... 2Preface ............................................................................................................................................................ 9
Release 2014.......................................................................................................................................... 91 GENERAL................................................................................................................................................... 11
1.1 Introduction.................................................................................................................................... 11Characterization of ADF ............................................................................................................... 11Fragments .................................................................................................................................... 12
1.2 Feature List .................................................................................................................................... 131.3 Technical remarks, Terminology ................................................................................................. 15
Density functional theory .............................................................................................................. 15The Kohn-Sham MO model.......................................................................................................... 16Basis functions and orbitals.......................................................................................................... 16Fit functions .................................................................................................................................. 19Three-step build-up of the bonding .............................................................................................. 20Transition State procedure ........................................................................................................... 21
1.4 Running the program.................................................................................................................... 22Execution of ADF ......................................................................................................................... 22Files .............................................................................................................................................. 23
1.5 ADF-GUI.......................................................................................................................................... 242 INPUT.......................................................................................................................................................... 25
2.1 Minimal input ................................................................................................................................. 252.2 Structure of the input .................................................................................................................... 25
Keywords...................................................................................................................................... 26Interpretation of Input ................................................................................................................... 27Link-in Input files .......................................................................................................................... 30Title, comment, layout of input ..................................................................................................... 30
2.3 Coordinates, basis sets, fragments............................................................................................. 31Atomic coordinates ....................................................................................................................... 31
Mixed Cartesian and Z-matrix coordinates.......................................................................... 33Orientation of Local Atomic Coordinates ............................................................................. 34ASCII Output Files with Atomic Coordinates ....................................................................... 34
Basis sets and atomic fragments ................................................................................................. 35Database of STO basis sets................................................................................................ 35
How TO make EVEN-tempered basis/fit sets? .......................................................... 37Available standard basis sets .............................................................................................. 40Automatic mode .................................................................................................................. 42Create mode........................................................................................................................ 44Ghost Atoms & Non-standard Chemical Elements ............................................................. 46Nuclear Model ..................................................................................................................... 48
What basis set should I use in ADF? ........................................................................................... 48ZORA or nonrelativistic calculation? ................................................................................... 48Large or small molecule? .................................................................................................... 49Frozen core or all-electron? ................................................................................................ 50Diffuse functions needed?................................................................................................... 50Normal or even-tempered basis? ........................................................................................ 51What accuracy do the basis sets give? ............................................................................... 51
Molecular fragments ..................................................................................................................... 53Fragment mode ................................................................................................................... 53Fragment files...................................................................................................................... 56
2.4 Model Hamiltonians....................................................................................................................... 57Electronic Configuration ............................................................................................................... 57
Charge and Spin ................................................................................................................. 58Orbital occupations: electronic configuration, excited states............................................... 59
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Aufbau, smearing, freezing ........................................................................................ 60Explicit occupation numbers....................................................................................... 61CHARGE vs. OCCUPATIONS ................................................................................... 63Create mode............................................................................................................... 63
Multiplet States .................................................................................................................... 63Multiplet energies ....................................................................................................... 64
Frozen core approximation.................................................................................................. 75Spin-polarized start-up potential.......................................................................................... 76
Spin-flip method for broken symmetries ..................................................................... 76Modify the starting potential ....................................................................................... 76
Unrestricted fragments ........................................................................................................ 78Remove Fragment Orbitals ................................................................................................ 79
Density Functional ........................................................................................................................ 80Exchange Correlation Potentials ......................................................................................... 80Defaults, special cases, simple input .................................................................................. 86
PBE functionals ................................................
