Table of Contents
ADF User's GuidePreface
ADF 2004.01
1 GENERAL
1.1 Introduction
Characterization of ADF
Functionality
Applicability
Model Hamiltonian
Analysis
Technical
Fragments
Basic atoms
Database
Automatic mode
Files
Standard output
Parallel execution
File names
1.2 Technical remarks, Terminology
Basis functions and orbitals
Cartesian function sets, spurious components
Frozen core: Core Orbitals and Core Functions
Symmetry
Orthonormal basis
Fragments
Summary of functions and orbitals
Fit functions
Three-step build-up of the bonding
Transition State procedure
2 INPUT
2.1 Introduction
Running the program
The run script 'start'
Files produced by ADF
Structure of the input
Delimiters
Uppercase and lowercase
Keywords
Irrelevant keys, misspelling of keys
Minimal input
Automatic mode
Create mode
Fragment mode
2.2 Main Options
Parallel Execution
Run Types
Runtype control and strategy parameters
Atomic Coordinates
Mixed Cartesian and Z-matrix coordinates
Geometry Optimization
Transition State
Linear Transit
Intrinsic Reaction Coordinate
IRC start direction
Forward / Backward IRC paths
Optimization: Special Features
geovar: constrained optimization, Linear (synchronious) Transit parameters
Constrained optimizations: coordinate types
Constrained optimizations: linear combinations of internal coordinates
Restrained optimizations
Symmetry versus constraints
Z-matrix and symmetry
Symmetry in a Linear Transit
Summary of geovar, optim, and atoms
Initial Hessian
Hessian values for selected coordinates
Frequencies
Accuracy
Cartesian versus Z-matrix displacements
Frequencies and GEOVAR keyword
Smoothing of Gradients
Fragments
Fragment files
QM/MM
Density Functional
Exchange Correlation Functionals
Defaults and special cases
Meta-GGA and hybrid energy functionals
Self-Interaction Correction
General remarks
Relativistic effects
Pauli
ZORA
Spin-Orbit coupling
Relativistic core potentials
Solvent effects: COSMO
Electric Field: Homogeneous and Point Charges
Orientation of the fields
Symmetry
Bonding energy
Polarizability and hyperpolarizability
Time-dependent DFT: Excitation Energies, (Hyper) Polarizabilities
General remarks on the use of the TDDFT Response and Excitation functionality
Excitation Input
Applications of the Excitation feature in ADF
Input description for the Response functionality
Analysis options for TDDFT implementation (excitation energies and polarizabilities)
ESR
Electronic Configuration
Spin: restricted vs. unrestricted
Unrestricted and Spin-Orbit Coupling
Net Charge and Spin polarization
Orbital occupations: electronic configuration, excited states
CHARGE vs. OCCUPATIONS
Create mode
Frozen core vs. pseudopotentials
Multiplet States
Precision and Self-Consistency
Numerical Integration
Frequencies
Self-adapting precision during optimizations
More integration options
SCF
Interpretation of Input
Units of length and angle
Expressions
Constants and functions
Strings
Where does parsing apply?
Constants vs. geometric parameters
Restarts
Check-point file
General remarks
The restart key
Structure of the restart file
Data on the restart file
SCF data
Coordinates
Hessian
Transition State
Linear Transit
IRC
Frequencies
Printed Output
Print / NoPrint
Debug
Eprint
Eprint subkeys vs. Print switches
Fit
Frag
Freq
GeoStep
NumInt
OrbPop
OrbPopER
Repeat
SCF
SFO
TransitionField
Other Eprint subkeys
Orbital Energies
Mulliken Population Analysis
Population Analysis per MO
Mayer Bond orders
Reduction of output
ASCII Output Files with Atomic Coordinates
2.3 More Options
General
Link-in Input files
Title and Comment
Layout of input
Geometry
Orientation of Local Atomic Coordinates
Symmetry
Ghost Atoms & Non-standard Chemical Elements
Creation
Use as fragment
Basis Set Superposition Error (BSSE)
Hamiltonian
Spin-polarized start-up potential
Unrestricted fragments
Remove Fragment Orbitals
Core Potentials
Properties and Analysis
NMR Chemical Shifts
NMR spin-spin coupling constants
EPR parameters
Localized Molecular Orbitals
NBO analysis
Bader's analysis
Precision
Numerical integration
Symmetric density fit
Fit integrals
Atomic radial grid
Dependency (basis set, fit set)
Control of Program Flow
Limited execution
Direct SCF: I/O vs. recalculation of data
Skipping
Ignore checks
Parallel Communication Timings
Technical Settings
Memory usage
Vector length
Tails
Linearscaling
All Points
Full SCF
Full Fock
Electrostatic interactions from Fit density
Save info
3 Recommendations, problems, Questions
3.1 Recommendations
Precision
Electronic Configuration
Spin-unrestricted versus spin-restricted, Spin states
Geometry Optimization
Bond angles of zero or 180 degrees
Sloppy modes
Step convergence
Basis Sets for Organic Molecules: Single-zeta vs. Double-zeta
Frequencies
Relativistic methods
3.2 Trouble Shooting
License file corrupt
Recover from Crash
Memory Management
Insufficient Space for Allocation
Iraloc: out of memory
Marker Error
SCF
No convergence
Convergence difficulties with spin-unrestricted calculations
Geometry Optimization
No convergence
Spurious jumps
Constraints are violated
Clearly wrong results (bond lengths)
Frequencies
Imaginary Frequencies
Geometry-displacement numbers in the logfile are not contiguous
Input ignored
SFO Populations
Error Aborts
Warnings
3.3 Questions
4 FILES
4.1 Parallel Execution
4.2 Standard output
Input Echo, Output Header
Main Job Characteristics
Build Info: Fragments and Function Sets
Technical Parameters
Computational Report
Results
Nuclear and Electronic Configuration
ESR Properties
Populations, Charge analysis
Dipole moment, Electrostatic potential
Energy and MO analysis
Summary of LT or IRC path(s)
Frequencies Results
Exit Procedure
Logfile
4.3 Log file
4.4 TAPE21
Contents of TAPE21
Section General
Section Geometry
Section Fragments
Section AtomTypes
Section Properties
Section Basis
Section Core
Section Fit
Section Num Int Params
Section Symmetry
Section Spin_orbit
Section Energy
Section Point_Charges
Section GeoOpt
Section TS
Section LT
Section IRC
Section IRC_Forward
Section IRC_Backward
Section Freq
Sections Ftyp n
Sections Ftyp n?
Section Freq Symmetry
Sections X
Sections Atyp n X
Section LqbasxLqfitx_xyznuc
Section GenptData
Section Multipole matrix elements
Section Irreducible matrix elements
Section ETS
Using Data from TAPE21
Representation of functions and frozen cores
Evaluation of the charge density and molecular orbitals
4.5 TAPE13
Contents of TAPE13
Section Fit
Section Freq
Section Geometry
Section GeoOpt
Section IRC
Section IRC_Forward
Section IRC_Backward
Section LT
Section TS
5 RESULTS
5.1 Properties
Electronic Configuration, Orbital Energies
Populations and Atomic Charges
Mulliken populations
Atom charges, fragment charges, and bond orders
Energy
Thermodynamics
5.2 Plots: Density, Potential, Orbitals
6 APPENDICES
6.1 Database
Data File for Create
Title
Basis functions
Core expansion functions
Core description
Fit functions
Start-up fit coefficients
Example: Calcium
6.2 Elements of the Periodic Table
6.3 Symmetry
Schönfliess symbols and symmetry labels
Molecular orientation requirements
7 References
