Table of Contents
ADF User's Guide
Table of Contents
Preface
ADF 2009.01
1 GENERAL
1.1 Introduction
Characterization of ADF
Functionality
Applicability
Model Hamiltonian
Analysis
Technical
Fragments
Basic atoms
Database
Automatic mode
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
1.3 Running the program
Execution of ADF
Parallel execution
Files
TAPE21 and logfile
Standard output
File names during parallel runs
2 INPUT
2.1 Introduction
Minimal input
2.2 Structure of the input
Delimiters
Uppercase and lowercase
Keywords
Irrelevant keys, misspelling of keys
Interpretation of Input
Units of length and angle
Expressions
Constants and functions
Strings
Where does parsing apply?
Constants vs. geometric parameters
Link-in Input files
Title and Comment
Layout of input
2.3 Coordinates, basis sets, fragments
Atomic coordinates
Mixed Cartesian and Z-matrix coordinates
Orientation of Local Atomic Coordinates
ASCII Output Files with Atomic Coordinates
Basis sets and atomic fragments
Automatic mode
Create mode
Ghost Atoms & Non-standard Chemical Elements
Automatic mode
Create mode
Use as fragment
Nuclear Model
Molecular fragments
Fragment mode
Fragment files
2.4 Model Hamiltonians
Electronic Configuration
Charge and Spin
Spin: restricted vs. unrestricted
Unrestricted and Spin-Orbit Coupling
Net Charge and Spin polarization
Orbital occupations: electronic configuration, excited states
Aufbau, smearing, freezing
Explicit occupation numbers
CHARGE vs. OCCUPATIONS
Create mode
Multiplet States
Frozen core approximation
Frozen core vs. pseudopotentials
Core Potentials
Spin-polarized start-up potential
Spin-flip method for broken symmetries
Modify the starting potential
Unrestricted fragments
Remove Fragment Orbitals
Density Functional
Exchange Correlation Potentials
Defaults, special cases, simple input
PBE functionals
SSB-D functional
Meta-GGA potentials
Model potentials
Hartree-Fock and (meta-)hybrid potentials
Simple XC potential input
Post-SCF energy functionals
GGA energy functionals
Meta-GGA and hybrid energy functionals
Self-Interaction Correction
General remarks
MM dispersion corrected functionals
MM dispersion corrected GGA-D functionals
MM dispersion (old implementation)
Relativistic effects
Pauli
ZORA
Spin-Orbit coupling
Relativistic core potentials
Solvents and other environments
COSMO: Conductor like Screening Model
Warning about frequencies with COSMO model
QM/MM: Quantum mechanical and Molecular Mechanics model
Quild: Quantum-regions Interconnected by Local Descriptions
DRF: Discrete Solvent Reaction Field Model
DRF Theory
Parameters needed in the DRF model
DRF input
EXTERNALS
FDE: Frozen Density Embedding
FDE Input
Fragment-specific FDE options
Kinetic energy approximants
General FDE options
Restrictions and pitfalls
SCRF: Self-Consistent Reaction Field
Introduction
Input
Electric Field: Homogeneous and Point Charges
Orientation of the fields
Symmetry
Bonding energy
Polarizability and hyperpolarizability
2.5 Structure and Reactivity
Run Types
Runtype control and strategy parameters
Geometry Optimization
Optim
Branch
Iterations
Hessupd
Converge
Step
DIIS
Externprogram
Inithess
Transition State
Linear Transit
Linear Transit (new branch)
Linear Transit (old branch)
Symmetry in a Linear Transit
Intrinsic Reaction Coordinate
IRC start direction
Forward / Backward IRC paths
Climbing-Image Nudged Elastic Band
Recommendations concerning the NEB method.
Special Features
Initial Hessian
Constrained optimizations, LT (new branch)
Constrained optimizations, LT (old branch), IRC, NEB
GEOVAR
coordinate types
linear combinations of constraint
Z-matrix and symmetry
Summary of geovar, optim, and atoms
Initial Hessian
Hessian values for selected coordinates
Restrained optimizations
Symmetry versus constraints
Frequencies
Analytical Frequencies
Numerical Frequencies
Input options
Cartesian versus Z-matrix displacements
Frequencies and GEOVAR keyword
Mobile Block Hessian (MBH)
MBH for partially optimized structures
Accuracy
MBH Notes
Thermodynamics
Accuracy
Isotope Shifts of Vibrational Frequencies
Scanning a Range of Frequencies
Smoothing of Gradients
DFTB
2.6 Spectroscopic properties
IR spectra, (resonance) Raman, VCD
IR spectra
Raman scattering
Raman Intensities for Selected Frequencies
Resonance Raman: excited-state finite lifetime
Resonance Raman: excited-state gradient
Resonance Raman for several excited states
Restrictions: (avoided) crossings between excited-states
Restrictions: results not trustworthy for higher excited states
Advanced Restarts
Resonance Raman Input options
Vibrational Circular Dichroism (VCD) spectra.
Time-dependent DFT
General remarks on the Response and Excitation functionality
Analysis options for TDDFT (excitation energies and polarizabilities)
Time-dependent Current DFT
Excitation energies: UV/Vis spectra, X-ray absorption, CD, MCD
Excitation energies, UV/Vis spectra
Tamm-Dancoff approximation
Accuracy and other technical parameters
Excitation energies for open-shell systems
Spin-flip excitation energies
Core Excitation energies, X-ray absorption
Excitation energies and Spin-Orbit coupling
Perturbative inclusion of spin-orbit coupling
Self-consistent spin-orbit coupling
CD spectra
MCD
Input options
Notes
Applications of the Excitation feature in ADF
(Hyper-)Polarizabilities, dispersion coefficients, ORD, magnetizabilities
Polarizabilities
Accuracy and convergence, RESPONSE key
Hyperpolarizabilities
Van der Waals dispersion coefficients
Optical rotation dispersion (ORD)
AORESPONSE: Lifetime effects, polarizabilities, ORD, magnetizabilities
AORESPONSE key
Technical paramaters and expert options
Applications of AORESPONSE
NMR
NMR Chemical Shifts
NMR spin-spin coupling constants
ESR/EPR g-tensor and A-tensor
EPR program
Nuclear Quadrupole Interaction (EFG)
Mössbauer spectroscopy
Isomer shifts
Quadrupole splittings
Nuclear resonance vibrational spectroscopy (NRVS)
2.7 Analysis
Molecules built from fragments
Bond energy analysis
Total energy evaluation
Symmetry
Localized Molecular Orbitals
Advanced charge density and bond order analysis
Mulliken populations
Hirshfeld charges, Voronoi deformation density
Multipole derived charges
Nalewajski-Mrozek Bond orders
Mayer Bond orders
ETS-NOCV: Natural Orbitals for Chemical Valence
NBO analysis
AIM: Atoms in Molecules
Bader atomic properties (grid based method)
ADF2AIM
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
Reduction of output
2.8 Accuracy and Efficiency
Precision and Self-Consistency
Numerical Integration
Integration key
Frequencies
Self-adapting precision during optimizations
More integration options
Atomic radial grid
SCF
Main options
Energy-DIIS
Augmented Roothaan-Hall (ARH)
Density fitting
Symmetric density fit
Fit integrals
True density in XC potential
Dependency (basis set, fit set)
Basis Set Superposition Error (BSSE)
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 and old gradients
Linearscaling
All Points
Full SCF
Full Fock
Electrostatic interactions from Fit density
Save info
2.9 Restarts
Restart files
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
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
SCF
No convergence
Convergence difficulties with spin-unrestricted calculations
Convergence difficulties with solvation 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 RESULTS
4.1 Results on standard output
Job Characteristics
Input Echo, Output Header
Main Job Characteristics
Build Info: Fragments and Function Sets
Technical Parameters
Computational Report
Exit Procedure
Logfile
Results
Nuclear and Electronic Configuration
Structure and Reactivity
Summary of LT or IRC path(s)
Frequencies Results
Spectroscopic Properties
Analysis
Mulliken populations
Hirshfeld charges, Voronoi deformation density
Multipole derived charges
Bond order analysis
Dipole moment, Quadrupole moment, Electrostatic potential
MO analysis
Bond energy analysis
4.2 Log file
4.3 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
4.4 TAPE13
Contents of TAPE13
Section Fit
Section Freq
Section Geometry
Section GeoOpt
Section IRC
Section IRC_Forward
Section IRC_Backward
Section LT
Section TS
4.5 Plots: Density, Potential, Orbitals
5 APPENDICES
5.1 Database
Data File for Create
Title
Basis functions
Core expansion functions
Core description
Fit functions
Start-up fit coefficients
Example: Calcium
5.2 Elements of the Periodic Table
5.3 Symmetry
Schönfliess symbols and symmetry labels
Molecular orientation requirements
6 References
Keywords
Index
