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Index
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General
Introduction
Functionality
Applicability
Model Hamiltonian
Analysis
Technical
Fragments
Basic atoms
Automatic mode
Slater-type basis sets
What’s new in ADF 2018
New features
New input parsing
New syntax for a few keywords
Strict parsing of input file
Feature List
Model Hamiltonians
Structure and Reactivity
Spectroscopic properties
Charge transport properties
Analysis
Accuracy and Efficiency
Technical remarks, Terminology
Density functional theory
The Kohn-Sham MO model
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
Acronyms
Fit functions
Three-step build-up of the bonding
Transition State procedure
Running the program
Execution of ADF
Files
TAPE21 and logfile
Standard output
File names during parallel runs
Input and Output
Minimal input
Shell script
Structure of the Input
Units of length and angle
Including an external file
Title, comment
General remarks on input structure and parsing
Keys
Blocks
Structure of the Output
Job Characteristics on standard Output
Log file, TAPE21, TAPE13
Coordinates, Basis sets, Fragments
Atomic coordinates
Cartesian
Z-matrix
Mixed Cartesian and Z-matrix
MOPAC format
Orientation of Local Atomic Coordinates
ASCII Output Files with Atomic Coordinates
Symmetry Key
Basis sets and atomic fragments
STO basis sets
Available basis sets
The Basis Key
Automatic mode
Create mode
Ghost Atoms, Non-standard Chemical Elements
Nuclear Model
Molecular fragments
Fragment mode
Fragment files
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. IRREPOCCUPATIONS
Create mode
Frozen core approximation
Spin-polarized start-up potential
Spin-flip method for broken symmetries
Modify the starting potential
Unrestricted fragments
Remove Fragment Orbitals
CDFT: Constrained Density Functional Theory
Density Functionals (XC)
LDA
GGA
MetaGGA
Hartree-Fock
Hybrid
Meta-Hybrid
Range separated hybrids
RangeSep + XCFun: Yukawa-range separated hybrids
Range-separated hybrids with LibXC
Notes on Hartree-Fock and (meta-)hybrid functionals
Model Potentials
Optimized effective potentials
XCFun
LibXC
Dispersion corrections
DFT-D3 functionals
DFT-D functionals
MM dispersion (old implementation)
dDsC: density dependent dispersion correction
DFT-ulg
DFT-MBD functionals
Self-Interaction Correction
Post-SCF energy functionals
GGA energy functionals
Meta-GGA and hybrid energy functionals
Post Hartree-Fock energy functionals
Relativistic effects
Pauli
ZORA
X2C and RA-X2C
Spin-Orbit coupling
Solvents and other environments
COSMO: Conductor like Screening Model
SM12: Solvation Model 12
QM/MM: Quantum mechanical and Molecular Mechanics model
Quild
DIM/QM: Discrete Interaction Model/Quantum Mechanics
DRF
Surface-enhanced response properties
Input options
EXTERNALS key for DRF
FDE: Frozen Density Embedding
Fragment-specific FDE options
Kinetic energy approximants
General FDE options
Frozen Density Embedding with External Orthogonality
FDE and (localized) COSMO
Subsystem TDDFT, coupled FDE
Restrictions and pitfalls
SCRF: Self-Consistent Reaction Field
VSCRF: Vertical Excitation Self-Consistent Reaction Field
3D-RISM: 3D reference Interaction Site Model
Electric Field: Homogeneous, Point Charges, Polarizability
Structure and Reactivity
Run Types
RunType control
Geometry Optimization
Convergence
Optimization strategy
Transition State
Transition State Reaction Coordinate (TSRC)
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, IRC, NEB, LT (old branch)
Restrained optimizations
Symmetry versus constraints
Frequencies
Analytical Frequencies
Numerical Frequencies
Mobile Block Hessian (MBH)
Thermodynamics
Gibbs free energy change for a gas phase reaction
Accuracy
Isotope Shifts of Vibrational Frequencies
Scanning a Range of Frequencies
Moments of inertia
Spectroscopic properties
IR spectra, (resonance) Raman, VROA, VCD
IR spectra
Raman scattering
Raman Intensities for Selected Frequencies
Resonance Raman: excited-state finite lifetime
Resonance Raman: excited-state gradient
VROA: (Resonance) vibrational Raman optical activity
Vibrational Circular Dichroism (VCD) spectra
Vibrationally resolved electronic spectra
Time-dependent DFT
General remarks on the Response and Excitation functionality
Analysis options for TDDFT (excitation energies and polarizabilities)
Time-dependent Current DFT
Magnetic properties within TDCDFT
Excitation energies: UV/Vis, X-ray, CD, MCD
Excitation energies, UV/Vis spectra
Tamm-Dancoff approximation
Full XC kernel
Plasmons in Molecules
Accuracy and other technical parameters
Excitation energies for open-shell systems
Spin-flip excitation energies
Select (core) excitation energies, X-ray absorption
State selective optimization excitation energies
Modify range of excitation energies
Excitations as orbital energy differences
Quadrupole intensities in X-ray spectroscopy
XES: X-ray emission spectroscopy
Excitation energies and Spin-Orbit coupling
Perturbative inclusion of spin-orbit coupling
Self-consistent spin-orbit coupling
Highly approximate spin-orbit coupled excitation energies open shell molecule
CV(n)-DFT: Constricted Variational DFT
TD-DFT+TB
sTDA, sTDDFT
CD spectra
MCD
Analysis
NTO: Natural Transition Orbitals
SFO analysis
Charge-transfer descriptors
Excited state (geometry) optimizations
Vibrationally resolved electronic spectra
FCF program: Franck-Condon Factors
Example absorption and fluorescence
Example phosphorescence
(Hyper-)Polarizabilities, ORD, magnetizabilities, Verdet constants
RESPONSE: (Hyper-)Polarizabilities, ORD
RESPONSE: Polarizabilities
RESPONSE: Accuracy and convergence
RESPONSE: Hyperpolarizabilities
RESPONSE: Optical rotation dispersion (ORD)
AORESPONSE: Lifetime effects, (Hyper-)polarizabilities, ORD, magnetizabilities, Verdet constants
AORESPONSE: Polarizabilities
AORESPONSE: Technical parameters and expert options
AORESPONSE: Damped First Hyperpolarizabilities
AORESPONSE: Damped Second Hyperpolarizabilities
AORESPONSE: ORD
AORESPONSE: magnetizabilities, Verdet constants, Faraday B term
AORESPONSE: Raman
Applications of AORESPONSE
POLTDDFT: Damped Complex Polarizabilities
UV/Vis spectra, CD spectra
Reduced fit set
Van der Waals dispersion coefficients
DISPER program: Dispersion Coefficients
Ligand Field and Density Functional Theory (LFDFT)
Introduction
Input description
NMR
NMR Chemical Shifts
Important notes
Input options
Paramagnetic NMR Chemical Shifts
NMR spin-spin coupling constants
Introduction
Input file for CPL: TAPE21
Running CPL
Practical Aspects
References
ESR/EPR
ESR/EPR g-tensor and A-tensor
ESR/EPR Q-tensor
ESR/EPR Zero-field splitting (D-tensor)
Nuclear Quadrupole Interaction (EFG)
Mössbauer spectroscopy
Transport properties
Charge transfer integrals (transport properties)
Charge transfer integrals with the TRANSFERINTEGRALS key
Charge transfer integrals with FDE
GREEN: Non-self-consistent Green’s function calculation
Introduction
Wide-band-limit
Input options
Output
GREEN with ADF-GUI
Analysis
Molecules built from fragments
Bond energy analysis
Bond energy details
Total energy evaluation
Interacting Quantum Atoms (IQA)
Localized Molecular Orbitals
Perturbed Localized Molecular Orbitals
Advanced charge density and bond order analysis
Charges, Populations, Bond orders
ETS-NOCV: Natural Orbitals for Chemical Valence
Adfnbo, gennbo: NBO analysis
NBO analysis of EFG, NMR chemical shifts, NMR spin-spin coupling
QTAIM: Atoms in Molecules
Bader atomic properties (grid based method)
ADF2AIM
Aromaticity index with QTAIM
adf2damqt: DAMQT interface
FOD: fractional orbital density
Controlling printed Output
Print / NoPrint
Debug
Eprint
Eprint subkeys vs. Print switches
Other Eprint subkeys
Reduction of output
Results on Output
Electronic Configuration
Mulliken populations
Hirshfeld charges, Voronoi deformation density
Multipole derived charges
Charge model 5
Bond order analysis
Dipole moment, Quadrupole moment, Electrostatic potential
Fragments and Basis Functions
MO analysis
Bond energy analysis
Densf: Volume Maps
Input
Result: TAPE41
Dos: Density of States
Introduction
Mulliken population analysis
Density of states analyses based on Mulliken population analysis
Generalizations of OPDOS, GPDOS, PDOS
Input
VCD Analysis: VCDtools
General Theory
General Coupled Oscillator Analysis
Available options
PyFrag: Activation Strain Model Analysis
Requirements
Running PyFrag
Specifying the Trajectory
Molecular Fragments
ADF Options
Analysis Options
Accuracy and Efficiency
Precision and Self-Consistency
SCF
Main options
Energy-DIIS
Augmented Roothaan-Hall (ARH)
Numerical Integration
Becke Grid
Voronoi grid (deprecated)
Atomic radial grid
Density fitting
Hartree-Fock RI scheme
Old Hartree-Fock RI scheme
Dependency (basis set, fit set)
Basis Set Superposition Error (BSSE)
Control of Program Flow
Limited execution
Skipping
Ignore checks
Parallel Communication Timings
Technical Settings
GPU Acceleration
Memory usage
Direct SCF: recalculation of data
Vector length
Tails and old gradients
Linearscaling
All Points
Full Fock
Electrostatic interactions from Fit density
Save info
Restarts
Restart files
The restart key
Structure of the restart file
Recommendations and Troubleshooting
Recommendations
Precision
Electronic Configuration
Spin-unrestricted versus spin-restricted, Spin states
What basis set should I use in ADF?
ZORA or non-relativistic calculation?
Large or small molecule?
Frozen core or all-electron?
Diffuse functions needed?
Normal or even-tempered basis?
What accuracy do the basis sets give?
Relativistic methods
Troubleshooting
License file corrupt
Recover from Crash
Memory Management
SCF troubleshooting
Geometry Optimization troubleshooting
New Branch
Old Branch
Very short bonds
Frequencies
Imaginary Frequencies
Geometry-displacement numbers in the logfile are not contiguous
Input ignored
SFO Populations
Error Aborts
Warnings
ADF as an AMS engine
Appendices
Basis set file format
Sections
Example of a basis set file: Calcium
Extending a basis set
Elements of the Periodic Table
Multiplet States
Multiplet energies
Dirac program: relativistic core potentials
Symmetry
Schönfliess symbols and symmetry labels
Molecular orientation requirements
Binary result files, KF browser
TAPE21
Contents of TAPE21
Using Data from TAPE21
TAPE13
KF browser
Error messages
Warnings
Examples
Introduction
Model Hamiltonians
Special exchange-correlation functionals
Example: Asymptotically correct XC potentials: CO
Example: Meta-GGA energy functionals: OH
Example: Hartree-Fock: HI
Example: B3LYP: H2PO
Example: Long-range corrected GGA functional LCY-BP: H2O
Example: Range-separated functional CAMY-B3LYP: H2O
Example: Grimme Molecular Mechanics dispersion-corrected functionals (DFT-D3-BJ)
Example: Density-Dependent Dispersion Correction (dDsC): CH4-dimer
Example: DFT-ulg Dispersion Correction: Benzene dimer T-shaped
ZORA and spin-orbit Relativistic Effects
Example: ZORA Relativistic Effects: Au2
Example: Spin-Orbit coupling: Bi and Bi2
Example: Spin-Orbit unrestricted non-collinear: Tl
Example: Excitation energies including spin-orbit coupling: AuH
Example: ZORA, X2C and RA-X2C: HgI2 = Hg + I2
Solvents, other environments
Example: COSMO: HCl
Example: solvation model SM12: Acetamide
Example: Electric Field, Point Charge(s): N2 and PtCO
Example: 3D-RISM: Glycine
Example: ReaxFF: ADF geometry optimization using ReaxFF forces
FDE: Frozen Density Embedding
Example: FDE: H2O in water
Example: FDE freeze-and-thaw: HeCO2
Example: FDE energy: NH3-H2O
Example: FDE energy: unrestricted fragments: Ne-H2O
Example: FDE geometry optimization: H2O-Li(+)
Example: Geometry optimization ICW FDE/sSDFT
Example: FDE NMR shielding: Acetonitrile in water
Example: FDE NMR spin-spin coupling: NH3-H2O
Example: Subsystem TDDFT, coupled FDE excitation energies
Example: FDE and COSMO: H2O-NH3
Example: FDE and COSMO: H2O-NH3
QM/MM calculations
Quild: Quantum-regions Interconnected by Local Descriptions
DIM/QM: Discrete Interaction Model/Quantum Mechanics
Example: DRF: hyperpolarizability H2O in water
Example: DRF: scripting tool
Example: CPIM: excitation energies N2 on silver cluster Ag68
Example: PIM: optimization N2 on silver cluster Ag68
Example: PIM: polarizability N2 on silver cluster Ag68
Example: PIM: Raman scattering N2 on silver cluster Ag68
Example: PIM: SEROA calculation N2 on silver cluster Ag68
Example: PIM: Multipole Method N2 on silver cluster Ag1415
Structure and Reactivity
Geometry Optimizations
Example: Geometry Optimization: H2O
Example: Restraint Geometry Optimization: H2O
Example: Constraint Geometry Optimization: H2O
Example: Initial Hessian
Example: Geometry optimization with an external electric field or point charges: LiF
Example: Excited state geometry optimization with a constraint: CH2O
Transition States, Linear Transits, Intrinsic Reaction Coordinates
Example: LT, Frequencies, TS, and IRC: HCN
Example: Transition state search with the CINEB method: HCN
Example: TS search using partial Hessian: C2H6 internal rotation
Example: Relativistic ZORA TS search: CH4 + HgCl2 <==> CH3HgCl + HCl
Example: TS reaction coordinate: F- + CH3Cl
Example: Constraint Linear Transit: H2O
Example: (non-)Linear Transit: H2O
Total energy, Multiplet States, S2, Localized hole, CEBE
Example: Total Energy calculation: H2O
Example: Multiplet States: [Cr(NH3)6]3+
Example: Calculation of S2: CuH+
Example: Localized Hole: N2+
Example: Broken spin-symmetry: Fe4S4
Example: Core-electron binding energies (CEBE): NNO
Example: Constrained DFT: H2O+ ... H2O
Spectroscopic Properties
IR Frequencies, (resonance) Raman, VROA, VCD, Franck-Condon factors
Example: Numerical Frequencies: NH3
Example: Numerical Frequencies, spin-orbit coupled ZORA: UF6
Example: Numerical Frequencies, accurate Hartree-Fock: H2O
Example: Numerical Frequencies of an excited state: PH2
Example: Analytic Frequencies: CN
Example: Analytic Frequencies: CH4
Example: Analytic Frequencies, scalar ZORA: HI
Example: Mobile Block Hessian (MBH): Ethanol
Example: Mobile Block Hessian: CH4
Example: Raman: NH3
Example: Resonance Raman, excited state finite lifetime: HF
Example: Resonance Raman, excited state gradient: Formaldehyde
Example: Vibrational Raman optical activity (VROA): H2O2
Example: Resonance VROA: H2O2
Example: Vibrational Circular Dichroism (VCD): NHDT
Example: Franck-Condon Factors: NO2
Excitation energies: UV/Vis spectra, X-ray absorption, CD, MCD
Example: Excitation energies and polarizability: Au2
Example: Excitation energies open shell molecule: CN
Example: Spin-flip excitation energies: SiH2
Example: TDHF excitation energies: N2
Example: excitation energies CAM-B3LYP: Pyridine
Example: CAMY-B3LYP excitation energies: H2O
Example: Full XC kernel in excitation energy calculation: H2O+
Example: Use of xcfun in excitation energy calculations: H2O
Example: Core excitation energies: TiCl4
Example: X-Ray Absorption and Emission Quadrupole Oscillator strengths at the Cl K-edge: TiCl4
Example: (Core) Excitation energies including spin-orbit coupling: Ne
Example: Excitation energies perturbative spin-orbit coupling: AgI
Example: Excitation energies including spin-orbit coupling for open shell: PbF
Example: Excited state geometry optimization: N2
Example: Spin-flip excited state geometry optimization: CH2
Example: Circular Dichroism (CD) spectrum: DMO
Example: CD spectrum, hybrid functional: Twisted ethene
Example: MCD: H2O
Example: MCD including zero-field splitting: H2O
Example: CV(n)-DFT excitation energies: Formamide
Example: TD-DFT+TB excitation energies: beta-Carotene
Example: sTDA excitation energies: Adenine
Example: sTDDFT excitation energies: Adenine
Example: sTDA excitation energies RS functional: Bimane
Example: sTDA excitation energies wB97: TCNE-Benzene
(Hyper-)Polarizabilities, dispersion coefficients, ORD, magnetizabilities, Verdet constants
Example: Polarizabilities including spin-orbit coupling: AgI
Example: damped first hyperpolarizability: LiH
Example: damped second hyperpolarizability: LiH
Example: Verdet constants: H2O
Example: Dispersion Coefficients: HF
Example: Optical Rotation Dispersion (ORD): DMO
Example: ORD, lifetime effects (key AORESPONSE): DMO
Example: Hyperpolarizabilities of He and H2
Example: Damped Verdet constants: Propene
Example: Static magnetizability: H2O
Example: Dynamic magnetizability: H2O
Example: Time-dependent current-density-functional theory: C2H4:
Example: Damped complex polarizabilities with POLTDDFT: Au10
Ligand Field DFT (LFDFT)
Example: Ligand Field DFT: Co 2+
Example: Ligan Field DFT: f-d transitions in Pr 3+
NMR chemical shifts and spin-spin coupling constants
Example: NMR Chemical Shifts: HBr
Example: NMR Chemical Shifts: HgMeBr
Example: NMR Chemical Shifts, SAOP potential: CH4
Example: NMR Nucleus-independent chemical shifts (NICS): PF3
Example: NMR with B3LYP: PF3
Example: NMR Spin-spin coupling constants: C2H2
Example: NMR Spin-spin coupling constants, hybrid PBE0: HF
Example: NMR Spin-spin coupling constants, finite nucleus: PbH4
ESR/EPR g-tensor, A-tensor, Q-tensor, ZFS
Example: ESR g-tensor, A-tensor, Q-tensor, D-tensor: HfV
Example: ESR g-tensor, A-tensor, self consistent spin-orbit coupling: VO
Example: ESR g-tensor, A-tensor, perturbative spin-orbit coupling: HgF
Example: ESR spin-restricted and spin-unrestricted: TiF3
Example: ESR, X2C and RA-X2C: PdH
Example: Zero-field splitting (ZFS), ESR D-tensor: NH
Example: ZFS D tensor, including direct electron spin-spin part: Phenylnitrene
EFG, Mössbauer
Example: Mössbauer spectroscopy: Ferrocene
Example: Mössbauer with X2C: Hg compounds
Transport properties
Charge transfer integrals (transport properties)
Example: Charge transfer integrals: AT base pair
Example: Charge transfer integrals with FDE: water dimer
Example: Charge Recombination Calculation of Toluene and TCNE
Example: XCDFT: Charge Separation of an ethylene dimer
Non-self-consistent Green’s function calculation
Example: DOS and transmission: Aluminium
Example: Gold electrodes
Example: Benzenedithiol junction: Wide-Band-Limit
Example: Benzenedithiol junction
Analysis
Fragment orbitals, bond energy decomposition, charge analysis
Example: Compound Fragments: Ni(CO)4
Example: Fragments: PtCl4H2 2-
Example: Spin-unrestricted Fragments: H2
Example: Bond Energy analysis open-shell fragments: PCCP
Example: Analysis of NaCl using ionic fragments: Na+ and Cl-
Example: Electron Pair bonding in NaCl: open shell fragments
Example: Bond Energy analysis meta-GGA, (meta-)hybrids: Zn2, Cr2, CrH
Example: Spin-Orbit SFO analysis: TlH
Example: (Perturbed) localized molecular orbitals in twisted Ethene
Example: Bader Analysis (AIM)
Example: Bader Reactivity
Example: Aromaticity indices with QTAIM
Example: Charge model 5 (CM5)
Example: Bond Orders
Example: NOCV: ethylene – Ni-diimina and H+ – CO
Example: NOCV: CH2 – Cr(CO)5
Example: NOCV: CH3 – CH3
Example: Activation Strain Model Analysis using PyFrag
DOS: Density of states
Example: Density of States: Cu4CO
Third party analysis software
Example: adf2aim: convert an ADF TAPE21 to WFN format (for Bader analysis)
Example: NBO analysis: adfnbo, gennbo
Example: NBO analysis: EFG
Example: NBO analysis: NMR chemical shift
Example: NBO analysis: NMR spin-spin coupling
Example: Multiple excited state gradients: H2O
Example: Calculation of overlap of primitive basis functions
Accuracy and Efficiency
BSSE, SCF convergence, Frequencies
Example: Basis Set Superposition Error (BSSE): Cr(CO)5 +CO
Example: Troubleshooting SCF convergence: Ti2O4
Example: Rescan frequencies: NH3
Speed
Example: Multiresolution
Scripting
Prepare an ADF job and generate a report
Example: Single point for multiple xyz files: Bakerset
Example: Basis set and integration accuracy convergence test: Methane
List of Examples
Required Citations
General References
Feature References
Coordinates, basis sets, fragments
Geometry optimizations, transition states, and reaction paths
Model Hamiltonians
Relativistic Effects
Solvents and other environments
Frequencies, IR Intensities, Raman, VCD
Time-Dependent DFT
LFDFT
NMR
ESR/EPR
Transport properties: Non-self-consistent Green’s function
Analysis
Accuracy and efficiency
External programs and Libraries
References
Keywords
ADF
Documentation
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ADF
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Recommendations and Troubleshooting
Recommendations and Troubleshooting
¶
Recommendations
Precision
Electronic Configuration
What basis set should I use in ADF?
Relativistic methods
Troubleshooting
License file corrupt
Recover from Crash
Memory Management
SCF troubleshooting
Geometry Optimization troubleshooting
Frequencies
Input ignored
SFO Populations
Error Aborts
Warnings