Keywords

Summary of all keywords

A1Fit
Type

Float

Default value

10.0

Unit

Angstrom

GUI name

Symmetric fit for distance >

Description

STO-Fit keyword: distance between atoms, in Angstrom. The symmetric fit approximation is applied only for atoms farther apart.

AccurateGradients
Type

Bool

Default value

No

Description

Print the nuclear gradients with more digits than usual.

AddDiffuseFit
Type

Bool

Default value

No

GUI name

Add diffuse functions in fit: Yes

Description

STO-Fit keyword: One can get more diffuse fit functions by setting this to True.

AllDipMat
Type

Bool

Default value

No

Description

Print all dipole matrix elements between occupied and virtual Kohn-Sham orbitals.

Allow
Type

String

Recurring

True

Description

Controlled aborts can in some cases be overruled. Of course, the checks have been inserted for good reasons and one should realize that ignoring them probably produces incorrect results or may lead to a program-crash.

AllPoints
Type

Bool

Default value

No

GUI name

Force use of all points

Description

ADF makes use of symmetry in the numerical integrations. Points are generated for the irreducible wedge, a symmetry unique sub region of space. Optionally the symmetry equivalent points are also used. This is achieved by setting this key to True.

AnalyticalFreq
Type

Block

Description

Define options for analytical frequencies.

B1Size
Type

Float

Description

Sparse grid max memory size

B1Thresh
Type

Float

Default value

1e-10

Description

MMGF_DENB1 and MMGF_GRADB1 cutoff values

Check_CPKS_From_Iteration
Type

Integer

Default value

1

Description

Solution of the CPKS equations is an iterative process, and convergence is achieved if the difference between U1 matrix of successive iterations falls below a certain threshold. This key can be used to determine at which iteration the checking should start taking place.

Debug
Type

String

Description

For debugging purposes. Options: fit, hessian, b1, densities, numbers, symmetry, all.

Hessian
Type

Multiple Choice

Default value

reflect

Options

[reflect, average]

Description

Whether the final Hessian is obtained by reflecting or averaging?

Max_CPKS_Iterations
Type

Integer

Default value

20

Description

Calculating the analytical frequencies requires the solution of the Coupled Perturbed Kohn-Sham (CPKS) equations, which is an iterative process. If convergence is not achieved (a warning will be printed in the output if this is the case) then this subkey can be used to increase the number of iterations, although convergence is not guaranteed. The user required accuracy of the U1 matrix, as well as the ADF integration accuracy, can effect the rates of convergence.

Print
Type

String

Description

Primarily for debugging purposes. Options: eigs, u1, parts. Choosing EIGS results in the print out of the MO eigenvectors, while U1 results in the print out of the U1 matrices. Except for small molecules this will result in a lot of data being output, and so they are not recommended. Choosing PARTS results in the print out of various sub-hessians that add up to give the final analytical hessian.

PrintNormalModeAnalysis
Type

Bool

Default value

No

Description

Request ADF to print analysis of the normal modes independently of AMS.

U1_Accuracy
Type

Float

Default value

5.0

Description

Solution of the CPKS equations is an iterative process, and convergence is achieved if the difference between U1 matrix of successive iterations falls below a certain threshold. This subkey can be used to set the threshold. The accuracy of the U1 will be 10**(-x). So, the higher the number the more accurate the U1 will be. While this parameter effects the accuracy of the frequencies, other factors also effect the accuracy of the frequencies, especially the ADF integration accuracy.

AOMat2File
Type

Bool

Default value

No

Description

Write PMatrix, Fock matrix, and overlap matrix on AO basis to file for future analysis purposes

AOResponse
Type

Block

Description

If the block key AORESPONSE is used, by default, the polarizability is calculated. Note that if the molecule has symmetry the key ALLPOINTS should be included

ALDA
Type

Bool

Default value

No

Description

Use ALDA only

Alpha
Type

Bool

Default value

No

Description

Calculate linear response

Beta
Type

Bool

Default value

No

Description

Will use 2n+1 rule to calculate beta.

CALCTRANSFORMPROP
Type

String

Description

Transformation Properties of Polarizabilities

Components
Type

String

Description

Limit the tensor components to the specified ones. Using this option may save the computation time. Options: XX, XY, XZ, YX, YY, YZ, ZX, ZY, ZZ

Cubic
Type

Bool

Default value

No

Description

Calculate cubic response

Damp
Type

Float

Default value

0.4

Description

Specify damping for non-acceleration iteration

Debug
Type

Integer

Default value

0

Description

Debug level for AOResponse.

DoNothing
Type

Bool

Default value

No

Description

Do nothing.

EFG
Type

Block

Description

Perform a Mulliken type analysis of the EFG principal components, and an analysis in terms of canonical MOs.

Atom
Type

Integer

Default value

1

Description

The number of the nucleus at which the EFG is to be analyzed (ADF input ordering).

NBO
Type

Bool

Default value

No

Description

Perform an NBO/NLMO analysis of the EFG. Requires a series of calculations. See documentation.

Nuc
Type

Integer

Default value

1

Description

The number of the nucleus at which the EFG is to be analyzed (ADF internal atom ordering).

Thresh
Type

Float

Default value

0.05

Description

The threshold for printing the EFG-NBO contributions. The default is 0.05, which means that only orbitals with absolute value contribution larger than 5% of the total EFG are printed. To increase the number of contributions printed, specify a smaller threshold.

EFIOR
Type

Bool

Default value

No

Description

EFISHG
Type

Bool

Default value

No

Description

EFPLOT
Type

Bool

Default value

No

Description

EL_DIPOLE_EL_DIPOLE
Type

String

Description

EL_DIPOLE_EL_OCTUPOLE
Type

String

Description

EL_DIPOLE_EL_QUADRUPOLE
Type

String

Description

EL_DIPOLE_MAG_DIPOLE
Type

String

Description

EL_DIPOLE_MAG_QUADRUPOLE
Type

String

Description

EL_QUADRUPOLE_EL_QUADRUPOLE
Type

String

Description

EL_QUADRUPOLE_MAG_DIPOLE
Type

String

Description

EOPE
Type

Bool

Default value

No

Description

FitAODeriv
Type

Bool

Default value

No

Description

Use FITAODERIV for Coulomb potential

Frequencies
Type

Float List

Default value

[0.0]

Unit

eV

Description

List of frequencies of incident light, the perturbing field, at which the time-dependent properties will be calculated.

GIAO
Type

Bool

Default value

No

Description

Use gauge-included atomic orbitals

Gamma
Type

Bool

Default value

No

Description

Will use 2n+1 rule to calculate gamma.

HirshPol
Type

Bool

Default value

No

Description

Hirshfeld Polarizability of fragments

IDRI
Type

Bool

Default value

No

Description

LifeTime
Type

Float

Unit

Hartree

Description

Specify the resonance peak width (damping) in Hartree units. Typically the lifetime of the excited states is approximated with a common phenomenological damping parameter. Values are best obtained by fitting absorption data for the molecule, however, the values do not vary a lot between similar molecules, so it is not hard to estimate values. A value of 0.004 Hartree was used in Ref. [266].

MAG_DIPOLE_MAG_DIPOLE
Type

String

Description

MagOptRot
Type

Bool

Default value

No

Description

Calculate magneto-optical rotation

MagneticPert
Type

Bool

Default value

No

Description

Use magnetic field as a perturbation

NBO
Type

Bool

Default value

No

Description

Perform NBO analysis

NoCore
Type

Bool

Default value

No

Description

if NOCORE is set we skip the core potential in diamagnetic term and/or in the unperturbed density of the CPKS solvers

OKE
Type

Bool

Default value

No

Description

OPTICALR
Type

Bool

Default value

No

Description

OpticalRotation
Type

Bool

Default value

No

Description

Calculate optical rotation

QuadBeta
Type

Bool

Default value

No

Description

Quadrupole operators with beta tensor

QuadPert
Type

Bool

Default value

No

Description

Calculate quadrupole-quadrupole polarizability

Quadratic
Type

Bool

Default value

No

Description

Calculate quadratic response

Quadrupole
Type

Bool

Default value

No

Description

Calculate dipole-quadrupole polarizability

Raman
Type

Bool

Default value

No

Description

SCF
Type

String

Description

Specify CPKS parameters such as the degree of convergence and the maximum number of iterations: NOCYC - disable self-consistence altogetherNOACCEL - disable convergence accelerationCONV - convergence criterion for CPKS. The default value is 10-6 . The value is relative to the uncoupled result (i.e. to the value without self-consistence).ITER - maximum number of CPKS iterations, 50 by default.Specifying ITER=0 has the same effect as specifying NOCYC.

SHG
Type

Bool

Default value

No

Description

STATIC
Type

Bool

Default value

No

Description

THG
Type

Bool

Default value

No

Description

TPA
Type

Bool

Default value

No

Description

Traceless
Type

Bool

Default value

No

Description

Traceless quadrupole tensors

VROA
Type

Bool

Default value

No

Description

Calculate Vibrational Raman Optical Activity.

VelocityOrd
Type

Bool

Default value

No

Description

Use VelocityOrd without GIAOs

XAlpha
Type

Bool

Default value

No

Description

Xalpha potential

Aromaticity
Type

Non-standard block

Description

Calculate aromaticity indicators, i.e. the matrix of localization/delocalization indices (LI-DI), Iring (ring index) and MCI (multi center index) aromaticity indices.

AtomicChargesTypeForAMS
Type

Multiple Choice

Default value

Mulliken

Options

[Mulliken, Hirshfeld, CM5, Voronoi, MDC-M, MDC-D, MDC-Q, QTAIM]

GUI name

Atomic charges for AMS

Description

Type of atomic charges to be used by AMS. Note that some of these atomic charges are computed and printed by default in ADF. Hirshfeld charges are available only for default atomic fragments.

Balance
Type

Bool

Default value

No

Description

Measure the actual speed of the nodes in the parallel machine

Basis
Type

Block

Description

Definition of the basis set

Core
Type

Multiple Choice

Default value

Large

Options

[None, Small, Large]

GUI name

Frozen core

Description

Select the size of the frozen core you want to use. Small and Large will be interpreted within the basis sets available (of the selected quality), and might refer to the same core in some cases. If you specify ‘None’ you are guaranteed to have an all-electron basis set.

CreateOutput
Type

Bool

Default value

No

Description

If true, the output of the atomic create runs will be printed to standard output. If false, it will be saved to the file CreateAtoms.out in the AMS results folder.

FitType
Type

Multiple Choice

Default value

Auto

Options

[Auto, SZ, DZ, DZP, TZP, TZ2P, QZ4P, TZ2P-J, QZ4P-J, AUG/ASZ, AUG/ADZ, AUG/ADZP, AUG/ATZP, AUG/ATZ2P, ET/ET-pVQZ, ET/ET-QZ3P, ET/ET-QZ3P-1DIFFUSE, ET/ET-QZ3P-2DIFFUSE, ET/ET-QZ3P-3DIFFUSE]

GUI name

STO fit set

Description

Expert option. Select the auxiliary fit to be used for STOfit or old Hartree-Fock RI scheme. The fit set for a given atom is taken from the all-electron basis set file for the specified choice, for the same element as the atom. By default (Auto) the fit set is taken from the original basis set file.

Path
Type

String

Description

The name of an alternative directory with basis sets to use. ADF looks for appropriate basis sets only within this directory. Default $AMSRESOURCES/ADF.

PerAtomType
Type

Block

Recurring

True

Description

Defines the basis set for all atoms of a particular type.

Core
Type

Multiple Choice

Options

[None, Small, Large]

Description

Size of the frozen core.

File
Type

String

Description

The path of the basis set file (the path can either absolute or relative to $AMSRESOURCES/ADF). Note that one should include ZORA in the path for relativistic calculations, for example ‘ZORA/QZ4P/Au’. Specifying the path to the basis file explicitly overrides the automatic basis file selection via the Type and Core subkeys.

Symbol
Type

String

Description

The symbol for which to define the basis set.

Type
Type

Multiple Choice

Options

[SZ, DZ, DZP, TZP, TZ2P, QZ4P, TZ2P-J, QZ4P-J, mTZ2P, AUG/ASZ, AUG/ADZ, AUG/ADZP, AUG/ATZP, AUG/ATZ2P, ET/ET-pVQZ, ET/ET-QZ3P, ET/ET-QZ3P-1DIFFUSE, ET/ET-QZ3P-2DIFFUSE, ET/ET-QZ3P-3DIFFUSE, Corr/TZ3P, Corr/QZ6P, Corr/ATZ3P, Corr/AQZ6P, POLTDDFT/DZ, POLTDDFT/DZP, POLTDDFT/TZP]

Description

The basis sets to be used.

PerRegion
Type

Block

Recurring

True

Description

Defines the basis set for all atoms in a region. If specified, this overwrites the values set with the Basis%Type and Basis%PerAtomType keywords for atoms in that region. Note that if this keyword is used multiple times, the chosen regions may not overlap.

Core
Type

Multiple Choice

Default value

Large

Options

[None, Small, Large]

Description

Size of the frozen core.

Region
Type

String

Description

The identifier of the region for which to define the basis set. Note that this may also be a region expression, e.g. ‘myregion+myotherregion’ (the union of two regions).

Type
Type

Multiple Choice

Default value

DZ

Options

[SZ, DZ, DZP, TZP, TZ2P, QZ4P, TZ2P-J, QZ4P-J, mTZ2P, AUG/ASZ, AUG/ADZ, AUG/ADZP, AUG/ATZP, AUG/ATZ2P, ET/ET-pVQZ, ET/ET-QZ3P, ET/ET-QZ3P-1DIFFUSE, ET/ET-QZ3P-2DIFFUSE, ET/ET-QZ3P-3DIFFUSE, Corr/TZ3P, Corr/QZ6P, Corr/ATZ3P, Corr/AQZ6P, POLTDDFT/DZ, POLTDDFT/DZP, POLTDDFT/TZP]

Description

The basis sets to be used.

Type
Type

Multiple Choice

Default value

DZ

Options

[SZ, DZ, DZP, TZP, TZ2P, QZ4P, TZ2P-J, QZ4P-J, mTZ2P, AUG/ASZ, AUG/ADZ, AUG/ADZP, AUG/ATZP, AUG/ATZ2P, ET/ET-pVQZ, ET/ET-QZ3P, ET/ET-QZ3P-1DIFFUSE, ET/ET-QZ3P-2DIFFUSE, ET/ET-QZ3P-3DIFFUSE, Corr/TZ3P, Corr/QZ6P, Corr/ATZ3P, Corr/AQZ6P, POLTDDFT/DZ, POLTDDFT/DZP, POLTDDFT/TZP]

GUI name

Basis set

Description

Select the basis set to use. SZ: Single Z DZ: Double Z DZP: Double Z, 1 polarization function TZP: Triple Z, 1 polarization function TZ2P: Triple Z, 2 polarization functions QZ4P: Quad Z, 4 pol functions, all-electron AUG: Augmented (extra diffuse functions) ET: Even tempered all electron basis sets J: Extra tight functions These descriptions are meant to give an indication of the quality, but remember that ADF uses Slater type functions. For standard calculations (energies, geometries, etc.) the relative quality is: SZ < DZ < DZP < TZP < TZ2P < ET-pVQZ < QZ4P The basis set chosen will apply to all atom types in your molecule. If no matching basis set is found, ADF will try to use a basis set of better quality. For TDDFT applications and small negatively charged atoms or molecules, use basis sets with extra diffuse functions. J: TZ2P-J, QZ4P-J: for use in ESR hyperfine or NMR spin-spin couplings. Use the Basis panel to select a basis set per atom type, and to see what basis set actually will be used.

BeckeGrid
Type

Block

Description

Options for the numerical integration grid.

AllowAngularBoost
Type

Bool

Default value

Yes

Description

Allow automatic augmentation of the Lebedev spherical grid for highly coordinated atoms.

InnerShellsPruning
Type

Bool

Default value

Yes

Description

Allow automatic pruning of the Lebedev spherical grid for shells close to the nuclei.

PartitionFunPruning
Type

Bool

Default value

Yes

Description

Allow pruning of integration points based on the value of the partition function.

QPNear
Type

Float

Unit

Angstrom

Description

Only relevant if you have specified point charges in the input file. ADF generates grids only about those point charges that are close to any real atoms. The criterion, input with the qpnear subkey, is the closest distance between the point charge at hand and any real atom.

Quality
Type

Multiple Choice

Default value

Auto

Options

[Auto, Basic, Normal, Good, VeryGood, Excellent]

Description

Quality of the integration grid. For a description of the various qualities and the associated numerical accuracy see reference. If ‘Auto’, the quality defined in the ‘NumericalQuality’ will be used.

QualityPerRegion
Type

Block

Recurring

True

Description

Sets the grid quality for all atoms in a region. If specified, this overwrites the globally set quality.

Quality
Type

Multiple Choice

Options

[Basic, Normal, Good, VeryGood, Excellent]

Description

The region’s integration grid quality.

Region
Type

String

Description

The identifier of the region for which to set the quality.

RadialGridBoost
Type

Float

Description

The number of radial grid points will be boosted by this factor. Some XC functionals require very accurate radial integration grids, so ADF will automatically boost the radial grid by a factor 3 for the following numerically sensitive functionals: LibXC M05, LibXC M05-2X, LibXC M06-2X, LibXC M06-HF, LibXC M06-L, LibXC M08-HX, LibXC M08-SO, LibXC M11-L, LibXC MS0, LibXC MS1, LibXC MS2, LibXC MS2H, LibXC MVS, LibXC MVSH, LibXC N12, LibXC N12-SX, LibXC SOGGA11, LibXC SOGGA11-X, LibXC TH1, LibXC TH2, LibXC WB97, LibXC WB97X, MetaGGA M06L, MetaHybrid M06-2X, MetaHybrid M06-HF, MetaGGA MVS.

BondOrders
Type

Block

Description

Options for the calculation of bond orders. Note: the calculation of bond orders should be requested via the Properties%BondOrders input option in the AMS driver input.

PrintAll
Type

Bool

Default value

No

Description

If ‘Yes’, all five types of bond orders (i.e. Nalewajski-Mrozek-1,2 & 3, Mayer and Gopinathan-Jug) will be printed to the output. Otherwise only the Nalewajski-Mrozek-3 and the type requested in BondOrders%TypeForAMS will be printed.

PrintTolerance
Type

Float

Default value

0.2

Description

Only bond orders larger than this threshold will be printed in the output (this treshold applies only to the printing in the ‘BOND-ORDER ANALYSIS’ section of the ADF output.

TypeForAMS
Type

Multiple Choice

Default value

Nalewajski-Mrozek-3

Options

[Nalewajski-Mrozek-1, Nalewajski-Mrozek-2, Nalewajski-Mrozek-3, Mayer, Gopinathan-Jug]

GUI name

Bond order type for AMS

Description

The type of bond order that will be saved, printed and used by AMS. Nalewajski-Mrozek-1,2: bond orders calculated from two-electron valence indices based on partitioning of tr(Delta_P^2) using 3-index set or 4-index set respectively. Nalewajski-Mrozek-3: bond-orders calculated from valence indices based on partitioning of tr(P*Delta_P). Inter-atomic bond orders are not defined with non-atomic fragments.

CalcOverlapOnly
Type

Bool

Default value

No

Description

Calculate overlaps of primitive basis and stops after computing them.

CDFT
Type

Block

Description

CDFT is a tool for carrying out DFT calculations in the presence of a constraint.

AllAtoms
Type

Bool

Default value

No

Description

If AllAtoms is true, then TheAtoms is overridden and all the atoms in the active fragment are included in the set.

AnalyticalHessian
Type

Integer

Default value

0

Description

This will calculate the analytical derivative of the energy w.r.t. the Lagrange multiplier up to the specified SCF iteration. This key is not recommended due to the high computational cost that comes with it. The calculation is equivalent to a ground state Hessian, and it is carried out with the full sum-over-states formula.

ChargeAndSpin
Type

Bool

Default value

No

Description

will constrain both the charge and the spin

Constraints
Type

Float List

Description

The values of the constraints. If CHARGEANDSPIN, constraints to the alpha and beta electrons need to be specified sequentially. One more electron => CONSTRAINTS -1.0. One less electron => CONSTRAINTS 1.0. If the CDFT type is EXCITEDCDFT, CONSTRAINTS=1.0 is recommended. Other values are technically possible but have not been tested yet.

DoNotOptimize
Type

Bool

Default value

No

Description

If true, the multipliers chosen in INITIALMULTIPLIERS will not be optimized and will be constant throughout the entire SCF procedure.

ExcitedCDFT
Type

Bool

Default value

No

Description

will generate an excited state with CONSTRAINTS number of ALPHA electrons constrained to occupy the virtual space of a ground state reference calculation. This is the essence of the eXcited Constrained DFT (XCDFT) method(P. Ramos, M. Pavanello, Low-lying excited states by constrained DFT, Journal of Chemical Physics 148, 144103 (2018) https://doi.org/10.1063/1.5018615) for the calculation of low-lying single excitations. XCDFT is found to correctly reproduce the energy surface topology at conical intersections between the ground state and the first singly excited state and can also accounts for the condensed phase effects in solvated chromophores where typical Delta SCF methods variationally collapse.

InitialMultipliers
Type

Float List

Description

If available, a guess for the Lagrange multipliers can be entered.

MaxIter
Type

Integer

Default value

200

Description

Maximum number of CDFT iterations. CDFT carries out a loop nested inside the SCF cycle.

Metric
Type

Bool

Default value

No

Description

Relevant for XCDFT. In the XCDFT method orthogonality is not imposed between the KS-orbitals of ground and excited states. If METRIC is specified, the degree of mixing of the single excited state with the ground state or high-order excitations is calculated. Three parameters are calculated: p, m and d. The parameters p and m will give information about the amount of mixing with the ground state, while parameter d will determine the mixing with high order excitations. Additional information about the origin of these parameters can be found in the literature (P. Ramos, M. Pavanello, Low-lying excited states by constrained DFT, Journal of Chemical Physics 148, 144103 (2018) https://doi.org/10.1063/1.5018615)

NAtomsPerSet
Type

Integer List

Description

The number of atoms in each moiety (set).

NConstraints
Type

Integer

Default value

1

Description

This specifies the number of sets of atoms to be considered. For example, if the user wishes to constrain a positive charge on one part of the system, and a negative charge on another part, NCONSTRAINTS should be set to two. There is no limit on the number of constraints. However, SCF convergence becomes an issue with more than 2 constraints. Note: NCONSTRAINTS>1 is untested.

OnlyCharge
Type

Bool

Default value

Yes

Description

Will constrain only the charge, letting spin relax (and potentially delocalize)

OnlySpin
Type

Bool

Default value

No

Description

Will constrain only the spin

PopType
Type

Multiple Choice

Default value

yukawalike

Options

[yukawalike, fuzzyvoronoibecke, fuzzyvoronoifermi]

Description

The population analysis chosen for determining the constraint.

Print
Type

Multiple Choice

Default value

low

Options

[low, medium, high]

Description

Print level and debugging.

SelfConsistent
Type

Bool

Default value

No

Description

Self-Consistent CDFT

StepSize
Type

Float

Default value

0.5

Description

The amount of the Lagrange multipliers step taken in each CDFT iteration

TheAtoms
Type

Integer List

Description

The atom numbers of the moieties in the input geometry order. If NCONSTRAINTS is larger than 1, the sets of atoms are entered as a single list.

Threshold
Type

Float

Default value

1e-10

Description

The threshold for convergence of the CDFT constraints. The tighter the SCF convergence criteria, the tighter the THRESHOLD should be.

CM5
Type

Bool

Default value

No

GUI name

: CM5 charges

Description

Calculate the charge model 5 (CM5) analysis.

comment
Type

Non-standard block

Description

The content of this block will be copied to the output header as a comment to the calculation.

ConceptualDFT
Type

Block

Description

Conceptual DFT Properties

AnalysisLevel
Type

Multiple Choice

Default value

Normal

Options

[Normal, Extended, Full]

Description

Set the level of the ConceptualDFT analysis: Normal - global descriptors only, Extended - both global and condensed (QTAIM) local descriptors, Full - all descriptors including non local ones.

AtomsToDo
Type

Integer List

GUI name

Include atoms

Description

Define a subset of atoms for which properties are calculated. If the [Domains] block is present then this list specifies which atoms are used to define the domains bounding box.

Domains
Type

Block

Description

Calculate integrated properties for the domains (same sign) of the dual descriptor.

Border
Type

Float

Default value

7.0

Unit

Bohr

Description

Set the extent of the Cartesian grid. Extent is the distance between a face of the grid’s bounding box and the most outlying atom in the corresponding direction. If the [AtomsToDo] key is present, the bounding box is created around the specified atoms.

Display
Type

Float

Default value

0.005

Description

Domains for which the integrated DD value is smaller (in magnitude) than the specified value are omitted from the printed output.

Enabled
Type

Bool

Default value

No

GUI name

Properties of reactivity domains

Description

Calculate properties of reactivity domains.

Ensemble
Type

Multiple Choice

Default value

Canonical

Options

[Canonical, GrandCanonical]

Description

Statistical ensemble for DD domains. Canonical: DD values are calculated using the statistical canonical ensemble. GrandCanonical: DD values are calculated using the statistical grand canonical ensemble. The grand canonical DD corresponds to (S^2 f(2) - (gamma/eta^3) f^0), where f(2) is the canonical DD, gamma and eta - the hyper-hardness and hardness of the chemical system, respectively, and f^0 is the mean Fukui function. This statistical ensemble is a natural choice when comparing two chemical systems with a different number of electrons.

Radius
Type

Float

Default value

0.0

Description

This option adds a sphere around each nucleus, excluding all points inside it. This can help to separate domains around an atom or to exclude core electrons. Be careful when using this option. In particular, the radius of the sphere should exceed two or three times the [Spacing] value to be effective. By default, no spheres are added.

Spacing
Type

Float

Default value

0.1

Unit

Bohr

Description

Specifies spacing (distance between neighboring points) of the rectangular Cartesian grid used when searching for DD domains. It may be useful to specify a smaller value (or increase the size of the grid, see [Border] key) if a substantial part of the electronic density is accounted for.

Threshold
Type

Float

Default value

0.001

Description

Arbitrary value of dual descriptor used to separate DD domains (values below this threshold are ignored).

Electronegativity
Type

Bool

Default value

No

GUI name

Atomic electronegativities

Description

Calculate atomic electronegativities. Requires an all-electron calculation (no frozen core), triggers the TotalEnergy and increases the [AnalysisLevel] to at least Extended.

Enabled
Type

Bool

Default value

No

GUI name

Conceptual DFT (FMO): Calculate

Description

Calculate Conceptual DFT properties.

ConstructPot
Type

Block

Description

Reads a density from a TAPE41 file and constructs numerically the corresponding potential to it

CPBasis
Type

Bool

Default value

Yes

Description

CPGrid
Type

Bool

Default value

No

Description

Converge
Type

Float

Default value

1e-06

Description

CutNegativeDens
Type

Float

Default value

0.0001

Description

Damp
Type

Float

Default value

1.0

Description

DensConv
Type

Float

Description

EigenShift
Type

Float

Default value

0.01

Description

FitBas
Type

Bool

Default value

Yes

Description

FixedLambda
Type

Bool

Default value

No

Description

ImportDens
Type

String

Description

Filename of density…

Lambda
Type

Float

Default value

0.01

Description

PotBas
Type

String

Description

Filename…

PotProj
Type

String

Description

ProjChange
Type

Float

Default value

-1.0

Description

ProjSmallDens
Type

Float

Default value

1e-50

Description

QPiterations
Type

Integer

Default value

1000

Description

SVD
Type

Bool

Default value

No

Description

SmallEigThresh
Type

Float

Default value

0.0001

Description

StartPot
Type

String

Description

Filename of potential…

StepSize
Type

Float

Default value

1.0

Description

TIKH
Type

Float

Default value

0.0

Description

CorePotentials
Type

Non-standard block

Description

With the key COREPOTENTIALS you specify the core file and (optionally) which sections pertain to the distinct atom types in the molecule.

Create
Type

String

Description

Keywords for create run. {Atomtype Datafile}

CurrentResponse
Type

Block

Description

CDSpec
Type

Bool

Default value

No

Description

Damping
Type

Float

Default value

0.0

Description

GTensor
Type

Bool

Default value

No

Description

Magnet
Type

Bool

Default value

No

Description

NCT
Type

Float

Default value

0.0

Description

NMRShielding
Type

Bool

Default value

No

Description

NoVK
Type

Bool

Default value

No

Description

PARTVK
Type

Float

Default value

1.0

Description

Parabolic
Type

Float

Default value

0.0

Description

QIANVignale
Type

Bool

Default value

No

Description

Static
Type

Bool

Default value

No

Description

CVNDFT
Type

Block

Description

The CVNDFT block key regulates the execution of the CV(n)-DFT code, which calculates the singlet or triplet electronic excitations for the closed shell molecules.

CV_DFT
Type

Block

Description

The simplest case: the TDDFT transition density U-vector is substituted into the infinite order CV(infinity)-DFT excitation energy

InitGuess
Type

Multiple Choice

Default value

TDDFT

Options

[TDDFT, SOR]

Description

Initial guess

DSCF_CV_DFT
Type

Block

Description

The simplest case: the TDDFT transition density U-vector is substituted into the infinite order CV(infinity)-DFT excitation energy

DampOrbRelax
Type

Float

Default value

0.2

Description

The mix_relax parameter defines the relative weight of the new relaxation vector that is added to the one from the previous iteration.

DampVariable
Type

Bool

Default value

No

Description

Damping condition

Damping
Type

Float

Default value

0.2

Description

Damping

InitGuess
Type

Multiple Choice

Default value

SOR

Options

[TDDFT, SOR]

Description

Initial guess

Optimize
Type

Multiple Choice

Default value

SVD

Options

[SVD, SOR, COL]

Description

Gradient optimization method

RelaxAlpha
Type

Integer

Default value

1

Description

The SCF cycle number at which the relaxation of alpha orbitals starts.

RelaxBeta
Type

Integer

Default value

1

Description

The SCF cycle number at which the relaxation of beta orbitals starts.

Iteration
Type

Integer

Default value

50

Description

The maximum number of iterations

RSCF_CV_DFT
Type

Block

Description

The simplest case: the TDDFT transition density U-vector is substituted into the infinite order CV(infinity)-DFT excitation energy

DampOrbRelax
Type

Float

Default value

0.2

Description

The mix_relax parameter defines the relative weight of the new relaxation vector that is added to the one from the previous iteration.

DampVariable
Type

Bool

Default value

No

Description

Damping condition

Damping
Type

Float

Default value

0.2

Description

Damping

InitGuess
Type

Multiple Choice

Default value

TDDFT

Options

[TDDFT, SOR]

Description

Initial guess

RelaxAlpha
Type

Integer

Default value

1

Description

The SCF cycle number at which the relaxation of alpha orbitals starts.

RelaxBeta
Type

Integer

Default value

1

Description

The SCF cycle number at which the relaxation of beta orbitals starts.

R_CV_DFT
Type

Block

Description

The simplest case: the TDDFT transition density U-vector is substituted into the infinite order CV(infinity)-DFT excitation energy

DampOrbRelax
Type

Float

Default value

0.2

Description

The mix_relax parameter defines the relative weight of the new relaxation vector that is added to the one from the previous iteration.

DampVariable
Type

Bool

Default value

No

Description

Damping condition

InitGuess
Type

Multiple Choice

Default value

TDDFT

Options

[TDDFT, SOR]

Description

Initial guess

RelaxAlpha
Type

Integer

Default value

1

Description

The SCF cycle number at which the relaxation of alpha orbitals starts.

RelaxBeta
Type

Integer

Default value

1

Description

The SCF cycle number at which the relaxation of beta orbitals starts.

SCF_CV_DFT
Type

Block

Description

The simplest case: the TDDFT transition density U-vector is substituted into the infinite order CV(infinity)-DFT excitation energy

DampVariable
Type

Bool

Default value

No

Description

Damping condition

Damping
Type

Float

Default value

0.2

Description

Damping

InitGuess
Type

Multiple Choice

Default value

TDDFT

Options

[TDDFT, SOR]

Description

Initial guess

Tolerance
Type

Float

Default value

0.0001

Description

The convergence criterion, i.e. the SCF-CV(infinity)-DFT procedure stops when the given accuracy is achieved.

Debug
Type

String

Recurring

True

Description

The amount of printed output is regulated with the keys Print, NoPrint, EPrint and Debug.

DensPrep
Type

Bool

Default value

No

Description

Undocumented option for FDE for sum-of-fragments density in SCF.

Dependency
Type

Block

Description

Enabled
Type

Bool

Default value

No

GUI name

Fix dependencies

Description

Used to make the basis or fit set linearly independent, up to the threshold specified below. This is typically important when you have many diffuse functions in your basis or fit set.

bas
Type

Float

Default value

0.0001

GUI name

Threshold for basis

Description

A criterion applied to the overlap matrix of unoccupied normalized SFOs. Eigenvectors corresponding to smaller eigenvalues are eliminated from the valence space. Note: if you choose a very coarse value, you will remove too many degrees of freedom in the basis set, while if you choose it too strict, the numerical problems may not be countered adequately.

eig
Type

Float

Default value

100000000.0

Description

Merely a technical parameter. When the DEPENDENCY key is activated, any rejected basis functions (i.e.: linear combinations that correspond with small eigenvalues in the virtual SFOs overlap matrix) are normally processed until diagonalization of the Fock matrix takes place. At that point, all matrix elements corresponding to rejected functions are set to zero (off-diagonal) and BigEig (diagonal). In AMSinput you must check the Fix Linear dependency check box for this option to be used.

fit
Type

Float

Default value

1e-10

GUI name

Threshold for fit

Description

Similar to Dependency%bas. The criterion is now applied to the overlap matrix of fit functions. The fit coefficients, which give the approximate expansion of the charge density in terms of the fit functions (for the evaluation of the coulomb potential) are set to zero for fit functions (i.e.: combinations of) corresponding to small-eigenvalue eigenvectors of the fit overlap matrix.

Diffuse
Type

Bool

Default value

No

Description

Adding diffuse integration points in case of the old Voronoi numerical integration grid.

DIMPAR
Type

Non-standard block

Description

In this block, the parameters for the DIM atoms are defined in DIM/QM calculations.

DIMQM
Type

Non-standard block

Description

Input for DIM/QM

DipoleLength
Type

Bool

Default value

No

Description

Use dipole-length elements for perturbing (external) integrals in CURRENT response

DipoleResponse
Type

Bool

Default value

No

Description

DumpBasisOnly
Type

Bool

Default value

No

Description

Dump basis and fit set files use for each atom.

ElectronTransfer
Type

Block

Description

Block key for charge transfer integrals with FDE.

CDFT
Type

Bool

Default value

No

Description

Debug
Type

Bool

Default value

No

Description

Disjoint
Type

Bool

Description

FDE
Type

Bool

Default value

No

Description

InvThr
Type

Float

Default value

0.001

Description

Joint
Type

Bool

Description

KNADD
Type

Bool

Default value

No

Description

NonCT
Type

Bool

Default value

No

Description

NumFrag
Type

Integer

Description

Print
Type

String

Description

EnergyFrag
Type

Non-standard block

Description

EPrint
Type

Block

Description

Print switches that require more specification than just off or on

AtomPop
Type

String

Description

Mulliken population analysis on a per-atom basis

BASPop
Type

String

Description

Mulliken population analysis on a per-bas-function basis

Eigval
Type

String

Description

One-electron orbital energies

Fit
Type

String

Description

Fit functions and fit coefficients

Frag
Type

String

Description

Building of the molecule from fragments

FragPop
Type

String

Description

Mulliken population analysis on a per fragment basis

Freq
Type

String

Description

Intermediate results in the computation of frequencies (see debug: freq).

GeoStep
Type

String

Description

Geometry updates (Optimization, Transition State, …)

NumInt
Type

String

Description

Numerical Integration

OrbPop
Type

Non-standard block

Description

(Mulliken type) population analysis for individual MOs

OrbPopEr
Type

String

Description

Energy Range (ER) in hartree units for the OrbPop subkey

Repeat
Type

String

Description

Repetition of output in Geometry iterations (SCF, optimization, …)

SCF
Type

String

Description

Self Consistent Field procedure

SFO
Type

String

Description

Information related to the Symmetrized Fragment Orbitals and the analysis

TF
Type

String

Description

Transition Field method

ESR
Type

Block

Description

Enabled
Type

Bool

Default value

No

Description

Calculate ESR (g- and/or A tensors)

ETSNOCV
Type

Block

Description

Perform ETS-NOCV analysis.

DEBUGTV
Type

Bool

Default value

No

Description

For T/V debugging

EKMin
Type

Float

Default value

2.0

Unit

kcal/mol

GUI name

Energy threshold

Description

The threshold for orbital interaction energy contributions corresponding to deformation density components originating from each NOCV-pairs

ENOCV
Type

Float

Default value

0.05

GUI name

NOCVs with ev larger than

Description

The threshold for NOCV-eigenvalues

Enabled
Type

Bool

Default value

No

Description

Perform ETS-NOCV analysis.

RhoKMin
Type

Float

Default value

0.01

GUI name

Population threshold

Description

The threshold for population analysis of each deformation density contribution in terms of individual SFOs.

TVanalysis
Type

Bool

Default value

No

GUI name

T/V analysis

Description

Perform T/V decomposition

ExactDensity
Type

Bool

Default value

No

Description

Use the exact density (as opposed to the fitted density) for the computation of the exchange-correlation potential

Excitations
Type

Block

Description

Excitation energies: UV/Vis

ALLXASMOMENTS
Type

Bool

Default value

No

Description

To be used in combination with XAS. This will print out all the individual transition moments used within the calculation of the total oscillator strength

ALLXASQUADRUPOLE
Type

Bool

Default value

No

Description

To be used in combination with XAS.This will print out the individual oscillator strength components to the total oscillator strength.

Allowed
Type

Bool

Default value

No

Description

Treat only those irreducible representations for which the oscillator strengths will be nonzero (as opposed to all)

AlsoRestricted
Type

Bool

Description

Include also excitation energies in which a spin-restricted exchange-correlation kernel is used

Analytical
Type

Bool

Default value

No

Description

The required integrals for the CD spectrum are calculated analytically, instead of numerically. Only used in case of CD spectrum

AsympCor
Type

Float

Default value

500.0

Description

BSE
Type

Bool

Default value

No

Description

Solve the static Bethe-Salpeter equation based on a GW calculation

CDSpectrum
Type

Bool

Default value

No

Description

Compute the rotatory strengths for the calculated excitations, in order to simulate Circular Dichroism (CD) spectra

DTensor
Type

String

Description

MCD gtensor

Davidson
Type

Non-standard block

Description

Use the Davidson procedure

Descriptors
Type

Bool

Default value

No

Description

Compute charge-transfer descriptors and SFO analysis

Descriptors_CT_AT_Rab
Type

Float

Default value

2.0

Description

Atomic distance criterion used for the calculation of CT_AT descriptors

ESESTDM
Type

Bool

Default value

No

Description

Compute transition dipole moments between excited states

Exact
Type

Non-standard block

Description

The most straightforward procedure is a direct diagonalization of the matrix from which the excitation energies and oscillator strengths are obtained. Since the matrix may become very large, this option is possible only for very small molecules

FullKernel
Type

Bool

Default value

No

Description

Use the non-ALDA kernel (with XCFUN)

GTensor
Type

String

Description

MCD gtensor

HDA
Type

Bool

Default value

No

GUI name

Hybrid diagonal approximation

Description

Activate the diagonal HF exchange approximation. This is only relevant if a (meta-)hybrid is used in the SCF.

HDA_CutOff
Type

Float

Default value

10000000.0

Unit

eV

GUI name

HDA cutoff

Description

This is cutoff based on differences in energy between eps_virt-eps_occ, to reduce number of diagonal HF exchange integrals.

Iterations
Type

Integer

Default value

200

Description

The maximum number of attempts within which the Davidson algorithm has to converge

KFWrite
Type

Integer

Default value

3

Description

If kfwrite is 0 then do not write contributions, transition densities, and restart vectors to TAPE21, since this can lead to a huge TAPE21, especially if many excitations are calculated. 3 means that contributions, transition densities, and restart vectors are written to TAPE21.

Lowest
Type

Integer List

Default value

[10]

GUI name

Number of excitations

Description

Number of lowest excitations to compute

MCD
Type

String

Description

TODO: Magnetic Circular Dichroism

NTO
Type

Bool

Default value

No

Description

Compute the Natural Transition Orbitals

N_HDA_integral
Type

Integer

Default value

1000000000

Description

Maximum number of HDA integrals

N_SFO
Type

Integer

Default value

40

Description

Number of SFO analyzed and printed

OnlySing
Type

Bool

Description

Compute only singlet-singlet excitations

OnlyTrip
Type

Bool

Description

Compute only singlet-triplet excitations

Orthonormality
Type

Float

Default value

1e-06

Description

The Davidson algorithm orthonormalizes its trial vectors. Increasing the default orthonormality criterion increases the CPU time somewhat, but is another useful check on the reliability of the results.

Residu
Type

Float

Default value

1e-06

Unit

Hartree

Description

SFOAnalysis
Type

Bool

Default value

No

Description

Do SFO analysis

SOSFreq
Type

Float

Description

STDA
Type

Bool

Default value

No

Description

Simplified Tamm-Dancoff approach

STDDFT
Type

Bool

Default value

No

Description

Simplified time-dependent DFT

ScaleCoul
Type

Float

Default value

1.0

Description

Scaling of Coulomb kernel with scale parameter

ScaleHF
Type

Float

Default value

1.0

Description

Scaling of the HF part of the kernel with scale parameter

ScaleXC
Type

Float

Default value

1.0

Description

Scaling of the XC-kernel (excluding a possible HF-part) with scale parameter

Select
Type

String

Description

Rather than selecting the first nmcdterm transitions for consideration individual transitions can be selected through the SELECT keyword

SingleOrbTrans
Type

Bool

Default value

No

Description

keyword to use only orbital energy differences

TD-DFTB
Type

Bool

Default value

No

Description

Use the molecular orbitals from a DFT ground state calculation as input to an excited state calculation with TD-DFTB coupling matrices

TDA-DFTB
Type

Bool

Default value

No

Description

Use the molecular orbitals from a DFT ground state calculation as input to an excited state calculation with TDA-DFTB coupling matrices

Tolerance
Type

Float

Default value

1e-06

Unit

Hartree

Description

Vectors
Type

Integer

Description

The maximum number of trial vectors in the Davidson algorithm for which space is allocated. If this number is small less memory will be needed, but the trial vector space is smaller and has to be collapsed more often, at the expense of CPU time. The default if usually adequate.

Velocity
Type

Bool

Default value

No

GUI name

Velocity representation

Description

Calculates the dipole-velocity representation of the oscillator strength. If applicable, the dipole-velocity representation of the rotatory strength is calculated. Default the dipole-length representation of the oscillator strength and rotatory strength is calculated

XAS
Type

Bool

Default value

No

Description

Calculation of the higher oder multipole moment integrals and the calculation of the quadrupole oscillator strengths. This will only print the total oscillator strength and the excitation energy.

ExcitedGO
Type

Block

Description

Excited state geometry optimization

ALLGRADIENTS
Type

Bool

Default value

No

Description

CPKS
Type

Block

Description

Some control parameters for the CPKS(Z-vector) part of the TDDFT gradients calculation

Eps
Type

Float

Default value

0.0001

Description

Convergence requirement of the CPKS

IterOut
Type

Integer

Default value

5

Description

Details of the CPKS calculation are printed every iter iterations

NoPreConiter
Type

Integer

Default value

200

Description

maximum number of iterations allowed for the unpreconditioned solver.

PreConiter
Type

Integer

Default value

30

Description

maximum number of iterations allowed for the preconditioned solver

EigenFollow
Type

Bool

Default value

No

Description

This key tries to follow the eigenvector in excited state geometry optimizations

Output
Type

Integer

Default value

0

Description

The amount of output printed. A higher value requests more detailed output

SING_GRADS
Type

Non-standard block

Description

Singlet
Type

Bool

Default value

Yes

Description

Singlet-singlet excitation is considered

State
Type

String

Description

Choose the excitation for which the gradient is to be evaluated: ‘State Irreplab nstate’. ‘Irreplab’ is the label from the TDDFT calculation. NOTE: the TDDFT module uses a different notation for some representation names, for example, A’ is used instead of AA. ‘nstate’: this value indicates that the nstate-th transition of symmetry Irreplab is to be evaluated. Default is the first fully symmetric transition.

TRIP_GRADS
Type

Non-standard block

Description

Triplet
Type

Bool

Default value

No

Description

Singlet-triplet excitation is considered

ExtendedPopan
Type

Bool

Default value

No

GUI name

: Extended population analysis

Description

Calculate the Mayer bond orders and Mulliken atom-atom populations per l-value

Externals
Type

Non-standard block

Description

Legacy support of the older DRF code.

FDE
Type

Block

Description

Frozen Density Embedding options

AMOLFDE
Type

Bool

Default value

No

Description

placeholder

CAPDENSCONV
Type

Float

Default value

0.0001

Description

placeholder

CAPPOTBASIS
Type

Bool

Default value

No

Description

placeholder

CAPPOTLINESEARCH
Type

Bool

Default value

No

Description

placeholder

CAPRADIUS
Type

Float

Default value

3.0

Description

placeholder

CJCORR
Type

Float

Default value

0.1

Description

Option to switch on a long-distance correction

Coulomb
Type

Bool

Description

Neglecting completely vt[rhoA,rhoB] (vt[rhoA,rhoB] equals zero) together with the exchange-correlation component of the embedding potential introduced by Wesolowski and Warshel.

Dipole
Type

Bool

Default value

No

Description

placeholder

E00
Type

Bool

Description

placeholder

EIGENSHIFT
Type

Float

Default value

0.01

Description

placeholder

ENERGY
Type

Bool

Default value

No

Description

placeholder

EXTERNALORTHO
Type

Float

Default value

1000000.0

Description

Used to specify the use of external orthogonality (EO) in the FDE block

EXTPRINTENERGY
Type

Bool

Default value

No

Description

placeholder

FULLGRID
Type

Bool

Default value

No

Description

placeholder

FreezeAndThawCycles
Type

Integer

Description

This keyword duplicates RelaxCycles

FreezeAndThawDensType
Type

String

Description

placeholder

FreezeAndThawPostSCF
Type

Bool

Description

This keyword duplicates RelaxPostSCF

GGA97
Type

Bool

Description

placeholder

GGAPotCFD
Type

String

Description

The correlation approximant is used in the construction of the embedding potential. The same correlation approximants as in the XC key are available.

GGAPotXFD
Type

String

Description

The exchange approximant is used in the construction of the embedding potential. The same exchange approximants as in the XC key are available.

LAMBDATIKH
Type

Float

Default value

0.1

Description

placeholder

LBDAMP
Type

Float

Default value

0.25

Description

placeholder

LBMAXSTEP
Type

Float

Default value

0.05

Description

placeholder

LLP91
Type

Bool

Description

placeholder

LLP91S
Type

Bool

Description

placeholder

NDSD
Type

String

Description

placeholder

NOCAPSEPCONV
Type

Bool

Description

placeholder

NOFDKERN
Type

Bool

Default value

Yes

Description

placeholder

OL91A
Type

Bool

Description

placeholder

OL91B
Type

Bool

Description

placeholder

ONEGRID
Type

Bool

Default value

No

Description

placeholder

P92
Type

Bool

Description

placeholder

PBE2
Type

Bool

Description

placeholder

PBE3
Type

Bool

Description

placeholder

PBE4
Type

Bool

Description

placeholder

PDFT
Type

Bool

Default value

No

Description

placeholder

PRINTEACHCYCLE
Type

Bool

Default value

No

Description

placeholder

PRINTRHO2
Type

Bool

Default value

No

Description

placeholder

PW86K
Type

Bool

Description

placeholder

PW91K
Type

Bool

Description

placeholder

PW91Kscaled
Type

Bool

Description

placeholder

RHO1FITTED
Type

Bool

Default value

No

Description

placeholder

RelaxCycles
Type

Integer

Default value

5

Description

This gives the maximum number of freeze-and-thaw cycles that are performed for this fragment. If the maximum number given in the FDE block is smaller, or if convergence is reached earlier, then fewer cycles are performed.

RelaxDensType
Type

String

Default value

Description

placeholder

RelaxPostSCF
Type

Bool

Default value

No

Description

this option is included, several post-SCF properties will be calculated after each freeze-and-thaw cycle. These are otherwise only calculated in the last cycle.

SCFCONVTHRESH
Type

Float

Default value

0.001

Description

placeholder

SDFTEnergy
Type

Bool

Default value

No

Description

placeholder

SHORTPRINTENERGY
Type

Bool

Default value

No

Description

placeholder

SMALLEIGTHRESH
Type

Float

Default value

0.0001

Description

placeholder

TF9W
Type

Bool

Description

placeholder

THAKKAR92
Type

Bool

Description

placeholder

THOMASFERMI
Type

Bool

Description

Local-density-approximation form of vt[rhoA,rhoB] derived from Thomas-Fermi expression for Ts[rho]

TW02
Type

Bool

Description

placeholder

WEIZ
Type

Bool

Description

placeholder

XCFun
Type

Bool

Default value

No

Description

Use XCFUN for nonadditive functionals

XCNAdd
Type

String

Description

FitExcit
Type

Bool

Default value

No

Description

ForceALDA
Type

Bool

Default value

No

Description

In spin-flip TDDFT, the XC kernel can be calculated directly from the XC potential. To use the LDA potential for the XC kernel, which roughly corresponds to the ALDA in ordinary TDDFT, one must specify the key

Fragments
Type

Non-standard block

Description

Definitions of the fragment type/files: {FragmentName FragmentFile}. In the block header one can specify the directory where the fragment files are located

FragMetaGGAToten
Type

Bool

Default value

No

GUI name

XC energy difference (for meta XCs): Use molecular grid

Description

By setting this to true the difference in the metahybrid or metagga exchange-correlation energies between the molecule and its fragments will be calculated using the molecular integration grid, which is more accurate than the default, but is much more time consuming.

FragOccupations
Type

Non-standard block

Description

Simulation of unrestricted fragments with the key FRAGOCCUPATIONS. Fragments need to be calculated spin-restricted. One can specify occupation numbers as if these fragments are calculated spin-unrestricted. The sum of spin-alpha and spin-beta occupations must, for each fragment orbital in each irrep separately, be equal to the total spin-restricted occupation of that orbital in the fragment.

FullFock
Type

Bool

Default value

No

GUI name

Full Fock matrix: Always

Description

Calculate the full Fock matrix each SCF iteration (instead of the difference with the previous cycle).

FullTotEn
Type

Bool

Default value

No

Description

Fuzzy_BO
Type

Bool

Default value

No

Description

GPU
Type

Block

Description

Set GPU options

Enabled
Type

Bool

Default value

No

GUI name

Use GPU

Description

Use a CUDA-compatible GPU.

UseDevices
Type

Integer List

GUI name

Only use devices

Description

Use only specified devices for this calculation. Multiple devices will be distributed evenly among MPI ranks.

GUIBonds
Type

Non-standard block

Description

The bonds used by the GUI (this does not affect the ADF calculation in any way)

GW
Type

Block

Description

Instruct ADF to perform a G0W0 calculation.

AdaptiveMixing
Type

Float List

Description

Requests to use adaptive mixing instead of DIIS and sets the staring mixing parameter for mixing of Green’s function in case of self-consistency. Adapative mixing is recommenened in case a qsGW calculation does not converge with DIIS. It is ignored in non-selfconsistent calculation and overwritten by DIIS when DIIS is also present.

AnalyticalIntegration
Type

Bool

Default value

No

Description

Use analytical integration to calculate the self-energy. Very slow, unless the system is very small but useful to check the accuracy of the frequency integration

Converge
Type

Block

Description

Sets convergence criteria for the GW calculation in self-consistent case

Density
Type

Float List

Default value

[1e-08, 1e-05]

Description

First Criterion for self-consistency procedure to terminate. Criterion is the trace of the density matrix. Ignored in non-selfconsistent Calculation and in eigenvalue self-consistent GW It is possible to run a qsGW calculation with an inner SCF loop which updates the static part of the elf-energy only. This can be useful to accelerate the convergence in case linear mixing is used. It is not recommended to use linear mixing, so it is also not recommened to use that inner loop as well. The second number in this list specifies the convergence criterion for the inner SCF loop.

HOMO
Type

Float

Default value

0.003

Unit

eV

GUI name

HOMO energy convergence

Description

Criterion for self-consistency procedure to terminate. The self-consistent GW calculation terminates, when the difference between the HOMO QP energies between 2 consecutive iterations is below this number. The LUMO energy converged faster than the HOMO energy so when the HOMO energy is converged according to this criterion, the LUMO energy will be converged as well. In non-selfconsistent Calculation, this criterion is ignored.

DIIS
Type

Integer

Default value

10

Description

Requests to use DIIS. This is the Default. Number of expansion coefficients can be requested as well. Ignored in non-selfconsistent calculation

Enabled
Type

Bool

Default value

No

GUI name

Calculate GW quasi-particle energies

Description

Enable the calculation of the GW quasi-particle energies.

FixedGrids
Type

Bool

Default value

No

Description

In a self-consistent GW calculation, do not recalculate Grids. Can be useful in case of convergence problems. Only relevant for qsGW and qsGW0. In case of evGW and evGW0, the grids are always kept fixed.

LinearMixing
Type

Float List

Description

Requests to use linear mixing instead of DIIS and sets the mixing parameter for linear mixing of Green’s function in case of self-consistency. It is ignored in non-selfconsistent calculation and overwritten by DIIS when DIIS is also present.

LinearizeQPequations
Type

Bool

Default value

No

Description

Instead of solving the non-linear QP equations in a G0W0 (or evGW calculation) by bisection exacly, linearize them by first-order Taylor expansion. This is not recommended since it does not save computational time when used together with analytical continuation (as implemented in AMS). It might however be useful for benchmarking or for validating results. If the results os the linearization differ by a lot (for instance, more than 0.1 eV in frontier QP energies) from the non-linearized results, this might indicate that the GW calculation is not reliable.

OffDiagonalEFermi
Type

Bool

Default value

No

Description

Analytically continue the off-diagonal elements of the KSF2 qsGW Hamiltonian at the Fermi-energy instead of omega=0. Typically leads to slightly lower QP energies, i.e. higher ionization potentials. The HOMO-LUMO gaps are typically not affected.

PrintAllSolutions
Type

Bool

Default value

No

Description

Print out all solutions for all requested states. Detects multiple solutions of the QP equations.

QPHamiltonian
Type

Multiple Choice

Default value

KSF2

Options

[KSF1, KSF2]

Description

The quasi-particle Hamiltonian can be constructed in different ways. KSF1 refers to the original construction by Kotani, Van Schilfgaarde anf Faleev (KSF) which is also implemented in TURBOMOLE. KSF2 refers to an alternative construction by KSF. KSF1 is not recommended since it is numerically less stable than KSF2. The results are typically very similar. The QP energies at which the matrix elements are evaluated can be tweaked further, see the two subsequent keys: However, KSF2 is recommened since it typically leads to QP energies with the best agreement with experiment. Ignored when not a quasi-particle self-consistent GW calculation is performed

ScissorShift
Type

Bool

Default value

No

Description

Only calculate the HOMO and LUMO QP energies and shift the remaining QP energies by the same amount. This is a rather crude approximaiton and not recommended. It might again be useful for benchmarking purposes.

SelfConsistency
Type

Multiple Choice

Default value

G0W0

Options

[G0W0, EVGW0, EVGW, QSGW0, QSGW]

Description

Sets the level of self-consistency in a GW calculation. G0W0 calculates a a on-shot, perturbative correction to the KS eigenvalues. In evGW and evGW0, the quasi-particle energies are updated until self-consistency is reached. evGW0 requests that the Green’s function is evaluated self-consistently but not the screened interaction. In qsGW, the density is updated as well, however, the self-energy is mapped to a static effective potential and the Dyson equation is solved by diagonalization instead of inversion. The results of a qsGW are independent of the choice of the underlying exchange-correlation functional and are usually the most accurate ones. The same is done in qsGW0, but the screened interaction is not updated.

SelfEnergy
Type

Multiple Choice

Default value

GW

Options

[HF, GW, G3W2]

Description

Controls the form of the self-energy. GW is the default and corresponds to the standard GW calculation. G3W2 is a GW calculation plus a perturbative second-order statically screened exchange correction (second order expansion in the self-energy). Note, that there the self-energy is always static.

nIterations
Type

Integer List

Default value

[10]

GUI name

Number of iterations

Description

The maximum number of iterations within the (partially or fully) self-consistent GW calculation has to converge. Ignored when Formalism is set to G0W0

nStates
Type

Integer

Default value

5

GUI name

N states

Description

Number of Quasiparticle States to be printed to output. The default is 5 states which in this case means that min(5, Number of particle states) occupied and min(5, Number of hole states) hole states are printed. The whole list of states can be printed by setting this parameter to -1’

preconditionQSGW
Type

Bool

Default value

No

Description

If true, the QSGW equations are solved but prior to each diagonalization, i.e. a G0W0 calculation is performed to find the optimal QP energies at which to analytically continue the self-energy. This is in principle a more consistent construction than KSF1 or KSF2 since the diagonal elements are consistent with G0W0. In KSF1 and KSF2, the diagonal elements are evaluated at the QP energies from the previous iteration which is equivalent to a zeroth-order Taylor expansion of the diaognal elements around the previous QP energies.Enabling this option typically leads to slightly lower QP energies.

GZip
Type

String

Description

GZip the corresponding tape (possibly working only for TAPE21)

HartreeFock
Type

Bool

Default value

No

Description

Compute hybrid meta-GGA energy functionals (if METAGGA key is True)

HFAtomsPerPass
Type

Integer

Description

Memory usage option for old HF scheme

HFMaxMemory
Type

Integer

Description

Memory usage option for old HF scheme

hydrogenbonds
Type

Bool

Default value

No

Description

Option for SFO population analysys to print small numbers.

IgnoreOverlap
Type

Bool

Default value

No

Description

Expert option. Ignore that atoms are close.

ImportEmbPot
Type

String

Description

File containing an external embedding potential (FDE calculations only)

ImportGrid
Type

String

Description

FDE option for importing numerical integration grid.

Integration
Type

Non-standard block

Description

Options for the obsolete Voronoi numerical integration scheme

IQA
Type

Block

Description

Total energy decomposition based on the interacting quantum atoms (IQA) approach and using QTAIM real-space partition.

AtomsToDo
Type

Integer List

GUI name

Include atoms

Description

Define a subset of atoms for which the IQA atom-atom interactions are calculated (no intra-atomic terms). If left empty, all atoms will be included (full IQA).

Enabled
Type

Bool

Default value

No

GUI name

Calculate: Interacting Quantum Atoms (IQA)

Description

Calculate the total energy decomposition using the interacting quantum atoms (IQA) approach and the QTAIM real-space partitioning.

Print
Type

Multiple Choice

Default value

verbose

Options

[normal, verbose]

Description

Minimal output (default) or verbose mode (detailed energy decomposition)

IrrepOccupations
Type

Non-standard block

Description

Explicit occupation numbers per irrep

IsotopicShift
Type

String

Description

Untested

LinearScaling
Type

Block

Description

Cutoff_Coulomb
Type

Float

Description

determines the radii for the fit functions in the evaluation of the (short-range part of) the Coulomb potential.

Cutoff_Fit
Type

Float

Description

determines how many atom pairs are taken into account in the calculation of the fit integrals and the density fit procedure. If the value is too low, charge will not be conserved and the density fitting procedure will become unreliable. This parameter is relevant for the timings of the FITINT and RHOFIH routines of ADF.

Cutoff_Multipoles
Type

Float

Description

determines the cut-offs in the multipole (long-range) part of the Coulomb potential

HF_Fit
Type

Float

Description

Parameter for HF exchange

Overlap_Int
Type

Float

Description

determines the overlap criterion for pairs of AOs in the calculation of the Fock-matrix in a block of points. Indirectly it determines what the cut-off radii for AO’s should be. The value of ovint has a strong influence on the timing for the evaluation of the Fock matrix, which is very important for the overall timings

ProgConv
Type

Float

Description

determines how the overall accuracy changes during the SCF procedure

LocOrb
Type

Non-standard block

Description

The computation of localized orbitals is controlled with this block-type key

MBPT
Type

Block

Description

Technical aspects of the MP2 algorithm.

Dependency
Type

Bool

Default value

Yes

Description

If true, to improve numerical stability, almost linearly-dependent combination of basis functions are removed from the Green’s function that are used in the MBPT equations. Disabeling this key is stringly discouraged. Its value can however be changed. The key to adjust this value is RiHartreeFock%DependencyThreshold

ExcludeCore
Type

Bool

Description

If active, excludes core states from the calculation of the optiomal imaginary time and frequency grids. The core states are still included in all parts of the calculations. In case a frozen care calculation is performed, this key is ignored. For MP2 and double hybrid calculation, it defauls to false. For RPA and GW calculations, it defaults to true.

FitSetQuality
Type

Multiple Choice

Default value

Auto

Options

[Auto, VeryBasic, Basic, Normal, Good, VeryGood]

Description

Specifies the fit set to be used in the MBPT calculation. ‘Normal’ quality is generally sufficient for basis sets up to and including TZ2P. For larger basis sets (or for benchmarking purposes) a ‘VeryGood’ fit set is recommended. Note that the FitSetQuality heavily influences the computational cost of the calculation. If not specified or ‘Auto’, the RIHartreeFock%FitSetQuality is used.

Formalism
Type

Multiple Choice

Default value

Auto

Options

[Auto, RI, LT, All]

Description

Specifies the formalism for the calculation of the MP2 correlation energy. ‘LT’ means Laplace Transformed MP2 (also referred to as AO-PARI-MP2), ‘RI’ means that a conventional RI-MP2 is carried out. If ‘Auto’, LT will be used in case of DOD double hybrids and SOS MP2, and RI will be used in all other cases. ‘All’ means that both RI and LT formalisms are used in the calculation. For a RPA or GW calculation, the formalism is always LT, irrespective of the formalism specified with this key.

FrequencyGridType
Type

Multiple Choice

Default value

LeastSquare

Options

[LeastSquare, GaussLegendre]

Description

Use Gauss-legendre grid for imaginary frequency integration in RPA and GW calculations instead of the usually used Least-Square optimized ones. Has the advantage that it can be systematically converged and an arbitrary number of grid points can be used. Typically more grid points will be needed to get the same level of accuracy. However, the convergence of the results with the size of the grid can be more systematic. These grids can only be used when Formalism is set to RI.

IntegrationQuality
Type

Multiple Choice

Options

[VeryBasic, Basic, Normal, Good, VeryGood]

Description

Specifies the integration quality to be used in the MBPT calculation. If not specified, the RIHartreeFock%IntegrationQuality is used.

SigmaFunctionalParametrization
Type

Multiple Choice

Default value

W1

Options

[W1, W2, S1, S2]

Description

Only relevant if a sigma-functional calculation is performed. Possible choices for the parametrization of the sigma-functional. Not all options are supported for all functionals.

ThresholdQuality
Type

Multiple Choice

Options

[VeryBasic, Basic, Normal, Good, VeryGood, Excellent]

Description

Controls the distances between atomic centers for which the product of two basis functions is not fitted any more. Especially for spatially extended, large systems, ‘VERYBASIC’ and ‘BASIC’ can lead to large computational savings, but the fit is also more approximate. If not specified, the RIHartreeFock%ThresholdQuality is used.

UseScaledZORA
Type

Bool

Default value

Yes

Description

If true, use the scaled ZORA orbital energies instead of the ZORA orbital energies in the MBPT equations.

nFrequency
Type

Integer

Default value

12

GUI name

Number of frequency points

Description

Number of imaginary frequency points. This key is only relevant for RPA and GW and will be ignored if used in an AO-PARI-MP2 calculation. 12 Points is the default for a RPA calculation. It is technically possible to use a different number of imaginary frequency points than for imaginary time. The maximum number of points which can be requested for imaginary frequency integration is 42. Important note: The computation time and memory requirements roughyl scale linearly with the number of imaginary frequency points. However, memory can be an issue for RPA and GW when the number of imaginary frequency points is high. In case a job crashes, it is advised to increase the number of nodes since the necessary memory distributes over all nodes.

nLambda
Type

Integer

Default value

1

GUI name

Number of lambda points

Description

Size of coupling constant integration grid for SOSEX variants in RPA. Default is 4 points

nTime
Type

Integer

GUI name

Number of time points

Description

Number of imaginary time points (only relevant in case the Laplace Transformed (LT) formalism is used). In the many-body-perturbation theory module in ADF, the polarizability (or Kohn-Sham density response function) is evaluated in imaginary time to exploit sparsity in the AO basis. For MP2, this is often referred to as a Laplace transform. For MP2, 9 points are the default. This is a safe choice, guaranteeing accuracies higher than 1 Kj/mol for most systems (For many simple organic systems, 6 points are sufficient for good accuracy). Only for systems with a very small HOMO-LUMO gap or low-lying core states (heavy elements starting from the 4th row of the periodic table) more points might be necessary. In principle, the same considerations apply for RPA and GW as well, however, the accuracy requirements are somewhat higher and 12 point are the default for RPA. In a GW calculation, the number of points is adjusted according to the numerical quality. Using less than 9 points is strongly discouraged except for the simplest molecules. In ADF2019, it can happen that the algorithm determining the imaginary time grid does not converge. In this case, the usual reason is that the number of points is too small and more points need to be specified. Starting from AMS2020, this does not happen any more. In case the imaginary time grid does not converge, the number of points is automatically adjusted until it does. The computation time of AO-PARI-MP2, RPA, and GW scales linearly with the number of imaginary time points.

MetaGGA
Type

Bool

Default value

No

Description

ModifyExcitation
Type

Block

Description

DipStrength
Type

Float

Description

GRIMMEAEX
Type

Float

Description

GRIMMEALPHA
Type

Float

Description

GRIMMEBETA
Type

Float

Description

GRIMMEDEMAX
Type

Float

Description

GRIMMEPERTC
Type

Bool

Description

GRIMMETPMIN
Type

Float

Description

HighExcit
Type

Float

Description

NOGRIMMEPERTC
Type

Bool

Description

NOverlap
Type

Integer

Default value

0

Description

OscStrength
Type

Float

Description

Use only pairs of an occupied and virtual orbital as guess vectors, for which the oscillator strength of the single-orbital transition is larger than this value

SetLargeEnergy
Type

Float

Default value

1000000.0

Unit

Hartree

Description

The orbital energies of the uninteresting occupied orbitals are changed to -epsbig Hartree, and the orbital energies of the uninteresting virtual orbitals are changed to epsbig Hartree

SetOccEnergy
Type

Float

Description

All occupied orbitals that have to be used will change their orbital energy to this value. In practice only useful if one has selected one occupied orbital energy, and one want to change this to another value. Default: the orbital energies of the occupied orbitals that are used are not changed.

UseOccRange
Type

Float List

Unit

Hartree

Description

Use only occupied orbitals which have orbital energies between the two numbers.

UseOccVirtNumbers
Type

Integer List

Description

Use only pairs of an occupied and virtual orbital as guess vectors, for which in the sorted list of the orbital energy differences, the number of the single-orbital transition is between the two numbers.

UseOccVirtRange
Type

Float List

Unit

Hartree

Description

Use only pairs of an occupied and virtual orbital, for which the orbital energy difference is between the two numbers

UseOccupied
Type

Non-standard block

Description

Use only the occupied orbitals which are specified

UseScaledZORA
Type

Bool

Default value

No

Description

Use everywhere the scaled ZORA orbital energies instead of the ZORA orbital energies in the TDDFT equations. This can improve deep core excitation energies. Only valid if ZORA is used.

UseVirtRange
Type

Float List

Unit

Hartree

Description

Use only virtual orbitals which have orbital energies between the two numbers

UseVirtual
Type

Non-standard block

Description

Use only the virtual orbitals which are specified

ModifyStartPotential
Type

Non-standard block

Description

Modify the starting spin-dependent potential for unrestricted calculations.

NoBeckeGrid
Type

Bool

Default value

No

Description

If true ADF will use the Voronoi numerical integration grid.

NoFDEPot
Type

Bool

Default value

No

Description

Expert FDE option.

NoPrint
Type

String

Recurring

True

Description

The amount of printed output is regulated with the keys Print, NoPrint, EPrint and Debug.

NoSharedArrays
Type

Bool

Default value

No

Description

To disable the use of shared memory.

NoSymFit
Type

Bool

Default value

No

Description

Do not use only an A1 symmetric fit.

NoTotEn
Type

Bool

Default value

No

Description

NuclearModel
Type

Multiple Choice

Default value

PointCharge

Options

[PointCharge, Gaussian]

Description

Model for the nuclear charge distribution. To see effects from your choice you will need to use a basis set with extra steep functions. For example you can find these in the ZORA/TZ2P-J basis directory.

NumericalQuality
Type

Multiple Choice

Default value

Normal

Options

[Basic, Normal, Good, VeryGood, Excellent]

Description

Set the quality of several important technical aspects of an ADF calculation (with the notable exception of the basis set). It sets the quality of: BeckeGrid (numerical integration) and ZlmFit (density fitting). Note: the quality defined in the block of a specific technical aspects supersedes the value defined in NumericalQuality (e.g. if I specify ‘NumericalQuality Basic’ and ‘BeckeGrid%Quality Good’, the quality of the BeckeGrid will be ‘Good’)

Occupations
Type

String

Description

Occupations options

OPop_Analysis
Type

String

Description

OrbitalsCoulombInteraction
Type

Integer List

Recurring

True

Description

Compute the Coulomb interaction energy between the density of two orbitals. After the key, specify the indices of the two orbitals for which you want to compute the Coulomb interaction energy. Can only be used for spin-restricted calculations. Cannot be used in case of Symmetry (use Symmetry NoSym).

OrthFragPrep
Type

Bool

Default value

No

Description

Expert FDE option.

PertLoc
Type

Block

Description

Perturbed localized molecular orbitals, correct to first order in an applied field, can be calculated in case of AORESPONSE. Can be used if the applied field changes the density in first order.

Alfa
Type

Bool

Default value

No

Description

Analyze the static or dynamic polarizability

BField
Type

Bool

Default value

No

Description

The perturbation is a magnetic field. Should be consistent with AORESPONSE

Beta
Type

Bool

Default value

No

Description

Analyze the optical rotation parameter beta. The relation to G’ is beta = -G’/omega. The optical rotation parameter beta is calculated directly and has a well-defined static limit, i.e. omega can be zero or non-zero

Diag
Type

Bool

Default value

Yes

Description

Only analyze the diagonal of the response tensor

Dynamic
Type

Bool

Default value

No

Description

Should be used for a frequency dependent perturbation field.

EField
Type

Bool

Default value

Yes

Description

The perturbation is an electric field

Fulltens
Type

Bool

Default value

No

Description

The full tensor is analyzed

GPrime
Type

Bool

Default value

No

Description

Analyze the G’ (gyration) tensor, for optical rotation dispersion. Requires a frequency dependent perturbation field, with a frequency (omega) unequal to zero.

Static
Type

Bool

Default value

Yes

Description

should be used for a static field

PolTDDFT
Type

Block

Description

POLTDDFT is a fast algorithm to solve the TDDFT equations in the space of the density fitting auxiliary basis set. The (real and imaginary part of the) diagonal of the polarizability tensor and rotatory strengths will be calculated, which can be used to calculate the photoabsorption and circular dichroism (CD) spectra.

Analysis
Type

Bool

Default value

No

Description

An analysis of the absortion and CD spectrum in terms of single orbital transitions.

CutOff
Type

Float

Default value

4.0

Unit

eV

Description

For a given point in the spectrum, only include pairs of an occupied and virtual orbital, for which the orbital energy difference is lower than the energy of the point in the spectrum plus cutoff.

Enabled
Type

Bool

Default value

No

GUI name

UV/Vis and CD spectrum

Description

Calculate UV/Vis and CD spectrum from the imaginary part of the polarizability tensor at any given photon energy. This avoids the bottleneck of Davidson diagonalization.

FreqRange
Type

Float List

Default value

[0.0, 5.0]

Unit

eV

Description

Specifies a frequency range of frequencies of incident light, the perturbing field, at which the complex dynamical polarizability will be calculated. 2 numbers: an upper and a lower bound. Use subkey NFreq to specify the number of frequencies.

HDA_fitted
Type

Bool

Default value

No

GUI name

Fitted HDA

Description

Use fit functions to calculate HDA (Hybrid diagonal approximation), only relevant for hybrids.

Irrep
Type

Non-standard block

Description

Subblock key for selecting which symmetry irreps of the excitations to calculate (all excitations by default). In the subkey data block list the symmetry irrep labels, like B1, for example

KGrid
Type

Float

Default value

9.0

Unit

eV

Description

Keyword KGRID is used to discretize the energy scale for calculating the complex dynamical polarizability. Only pairs of an occupied and virtual orbital are included, for which the orbital energy difference is lower than this value. Use key NGRID to set the number of points within the energy grid.

Lambda
Type

Float

Default value

1.0

Description

Jacob’s scaling factor for the study of plasmonic resonances. This factor, 0<lambda<1, turns on the coupling matrix K.

Lifetime
Type

Float

Default value

0.1

Unit

eV

Description

Specify the resonance peak width (damping). Typically the lifetime of the excited states is approximated with a common phenomenological damping parameter. Values are best obtained by fitting absorption data for the molecule, however, the values do not vary a lot between similar molecules, so it is not hard to estimate values.

NFreq
Type

Integer

Default value

100

Description

NFreq is the number of frequencies of incident light, the perturbing field, at which the complex dynamical polarizability will be calculated. Use FreqRange to specify the frequency range.

NGrid
Type

Integer

Default value

180

Description

Ngrid is the number of points within the energy grid.

N_FitOrb
Type

Integer

Default value

1000000000

Description

The number of vectors containing the coefficients we use to expand the projection of each fitting function over the electron density (of a particular molecular orbital) as a linear combination of overlap matrices between fitting functions pair

N_HDA_integral
Type

Integer

Default value

1000000000

Description

N_SubMatricesAk
Type

Integer

Default value

1000000000

Description

Print_Int_Time
Type

Integer

Default value

0

Description

Print detailed timing during calculation of integrals of Tape63 and Tape64

RegionsForAnalysis
Type

String

Description

Names of regions for analysis per region using the fragment projection analysis approach. Will split the absortion and CD spectrum in region_i -> region_j terms.

Velocity
Type

Bool

Default value

No

GUI name

Velocity representation

Description

If True, ADF calculates the dipole moment in velocity gauge. If false: dipole-length representation is used

Print
Type

String

Recurring

True

Description

The amount of printed output is regulated with the keys Print, NoPrint, EPrint and Debug.

QMFQ
Type

Block

Description

Block input key for QM/FQ(FMu).

AtomType
Type

Block

Recurring

True

Description

Definition of atomic types in MM environment

Alpha
Type

Float

Description

Polarizability of FQFMU atom

Charge
Type

Float

Description

MM fixed charge (non-polarizable only)

Chi
Type

Float

Description

Electronegativity of FQ atom

Eta
Type

Float

Description

Chemical Hardness of FQ atom

Symbol
Type

String

Description

Symbol associated with atom type

Coords
Type

Non-standard block

Description

Coordinates and fragment information (FQ only)

FDERESP
Type

Bool

Default value

No

Description

In response calculations (TD), the polarization contribution of the FDE part is introduced at the FQ level [See F. Egidi et al. J. Chem. Phys. 2021, 154, 164107].

Forcefield
Type

Multiple Choice

Default value

FQ

Options

[FQ, FQFMU]

Description

Version of the FQ family of polarizable forcefields

Frozen
Type

Bool

Default value

No

Description

Expert option. Do not introduce polarization effect in response calculations.

Kernel
Type

Multiple Choice

Default value

OHNO

Options

[OHNO, COUL, GAUS]

Description

Expert option. KERNEL can be used to choose the functional form of the charge-charge interaction kernel between MM atoms. Recommended is to use the default OHNO. The COUL screening is the standard Coulomb interaction 1/r. The OHNO choice introduce the Ohno functional (see [K. Ohno, Theoret. Chim. Acta 2, 219 (1964)]), which depends on a parameter n that is set equal to 2. Finally, the GAUS screening models each FQ charge by means of a spherical Gaussian-type distribution, and the interaction kernel is obtained accordingly. For QM/FQFMU only GAUS SCREEN is implemented.

MolCharge
Type

Float

Default value

0.0

Description

Total charge of each fragment (FQ only)

QMSCREEN
Type

Multiple Choice

Default value

GAUS

Options

[ERF, EXP, GAUS, NONE]

Description

Expert option. QMSCREEN can be used to choose the functional form of the charge-charge interaction kernel between MM atoms and the QM density. The screening types available are ERF (error function), EXP (exponential), GAUS (Gaussian), or NONE. The default is GAUS.

QMSCREENFACTOR
Type

Float

Default value

0.2

Description

Expert option. Sets the QM/MM interaction kernel screening length. Recommended is to use the default value 0.2 with the GAUS QM/MM screening function.

Repulsion
Type

Block

Description

Definition of parameters for Pauli repulsion (see JCTC ….)

AtomDistance
Type

Float

Default value

5.0

Description

Each fictitious Slater function is added only if the associated MM atom is closer than the AtomDistance threshold (in Angstrom) to a QM atom

Basis
Type

Block

Recurring

True

Description

Slater type basis function to add on a specific atom type in the environment.

AngMom
Type

Integer

Description

Angular momentum

AtomType
Type

String

Description

Atom Type on which the basis function has to be added

Coeff
Type

Float

Description

Coefficient of the basis function

Exp
Type

Float

Description

Exponent of the basis function

QTAIM
Type

Block

Description

This block is used to request a topological analysis of the gradient field of the electron density, also known as the Bader’s analysis. If this block is specified without any sub-key, only local properties are calculated.

AnalysisLevel
Type

Multiple Choice

Default value

Normal

Options

[Normal, Extended, Full]

Description

Set the level of the QTAIM analysis: Normal - topology analysis and properties at the density critical points, Extended - same as Normal plus condensed atomic descriptors, Full - same as Extended plus non-local descriptors.

AtomsToDo
Type

Integer List

GUI name

Include atoms

Description

List of atoms for which condensed descriptors are to be calculated. By default all atoms are included.

Enabled
Type

Bool

Default value

No

GUI name

Perform QTAIM analysis

Description

Calculate QTAIM (also known as Bader) properties.

Energy
Type

Bool

Default value

No

GUI name

Atomic energies

Description

Calculate atomic energies. Requires an all-electron calculation (no frozen core), triggers the TotalEnergy and increases the [AnalysisLevel] to at least Extended.

Source
Type

Bool

Default value

No

GUI name

Source Function

Description

Calculate the Source Function at BCPs and RCPs.

Spacing
Type

Float

Default value

0.5

Unit

Bohr

Description

Specifies spacing of the initial Cartesian grid when searching for critical points. It may be useful to specify a smaller value than the default if some critical points are missed. This will result in a more accurate but slower calculation.

QTens
Type

Bool

Default value

No

Description

Calculate the the Nuclear Electric Quadrupole Hyperfine interaction (Q-tensor, NQCC, NQI), related to the Electric Field Gradient (EFG).

RadialCoreGrid
Type

Block

Description

For each atom the charge densities and the coulomb potentials of frozen core and valence electrons are computed in a radial grid. The radial grid consists of a sequence of r-values, defined by a smallest value, a constant multiplication factor to obtain each successive r-value, and the total number of points. Equivalently it can be characterized by the smallest r-value, the largest r-value, and the number of points; from these data the program computes then the constant multiplication factor.

NRad
Type

Integer

Default value

5000

Description

The number of radial grid points

RMax
Type

Float

Default value

100.0

Unit

Angstrom

Description

The largest distance in the radial grid

RMin
Type

Float

Default value

1e-06

Unit

Angstrom

Description

The shortest distance used in the radial grid

Relativity
Type

Block

Description

Options for relativistic effects.

Formalism
Type

Multiple Choice

Default value

ZORA

Options

[Pauli, ZORA, X2C, RA-X2C]

Description

Note that if Level is None, no relativistic effects are taken into account, irrespective of the chosen formalism. Pauli stands for the Pauli Hamiltonian. ZORA means the Zero Order Regular Approximated Hamiltonian, recommended. X2C and RA-X2C both stand for an exact transformation of the 4-component Dirac equation to 2-components. X2C is the modified Dirac equation by Dyall. RA-X2C is the regular approach to the modified Dirac equation.

Level
Type

Multiple Choice

Default value

Scalar

Options

[None, Scalar, Spin-Orbit]

GUI name

Relativity

Description

None: No relativistic effects. Scalar: Scalar relativistic. This option comes at very little cost. Spin-Orbit: Spin-orbit coupled. This is the best level of theory, but it is (4-8 times) more expensive than a normal calculation. Spin-orbit effects are generally quite small, unless there are very heavy atoms in your system, especially with p valence electrons (like Pb). See also the SpinOrbitMagnetization subkey.

Potential
Type

Multiple Choice

Default value

MAPA

Options

[MAPA, SAPA]

Description

Starting from ADF2017 instead of SAPA (the Sum of neutral Atomical potential Approximation) MAPA is used by default for ZORA. The MAPA (the Minumium of neutral Atomical potential Approximation) at a point is the minimum of the neutral Atomical potentials at that point. Advantage of MAPA over SAPA is that the gauge dependence of ZORA is reduced. The ZORA gauge dependency is small for almost all properties, except for the electron density very close to a heavy nucleus. The electron density very close to a heavy nucleus can be used for the interpretation of isomer shifts in Mossbauer spectroscopy.

SpinOrbitMagnetization
Type

Multiple Choice

Default value

CollinearZ

Options

[NonCollinear, Collinear, CollinearX, CollinearY, CollinearZ]

Description

Relevant only for spin-orbit coupling and if unrestricted key has been activated. Most XC functionals have as one ingredient the spin polarization in case of unrestricted calculations. Normally the direction of the spin quantization axis is arbitrary and conveniently chosen to be the z-axis. However, in a spin-orbit calculation the direction matters, and it is arbitrary to put the z-component of the magnetization vector into the XC functional. There is also the exotic option to choose the quantization axis along the x or y axis. It is also possible to plug the size of the magnetization vector into the XC functional. This is called the non-collinear approach. - NonCollinear: the non-collinear method. - CollinearXYZ: use the x, y, or z component as spin polarization for the XC functional. - Collinear: the same as CollinearZ.

RemoveAllFragVirtuals
Type

Bool

Default value

No

Description

Remove all virtual fragment orbitals.

RemoveFragOrbitals
Type

Non-standard block

Description

Block key to remove selected virtual fragment orbitals.

Response
Type

Block

Description

The calculation of frequency-dependent (hyper)polarizabilities and related properties (Raman, ORD)

ALLCOMPONENTS
Type

Bool

Description

ALLHYPER
Type

Bool

Description

ALPHAINANG
Type

Bool

Description

ANALYTIC
Type

Bool

Description

AllCycles
Type

Bool

Default value

No

Description

Convergence printout

AllTensor
Type

Bool

Default value

No

Description

Higher dispersion coefficients are also calculated

C8
Type

Bool

Description

CUTTAILS
Type

Bool

Description

DYNAHYP
Type

Bool

Description

Dipole
Type

Bool

Description

DmpDII
Type

Float

Default value

0.8

Description

DmpRsp
Type

Float

Default value

0.9

Description

ERABSX
Type

Float

Default value

1e-06

Description

ERRALF
Type

Float

Default value

1e-05

Description

ERRTMX
Type

Float

Default value

1e-06

Description

EpsRho
Type

Float

Description

Rho threshold

FXCALPHA
Type

Float

Description

FXCDRCONV
Type

Bool

Description

FXCLB
Type

Bool

Description

Frequencies
Type

Float List

Default value

[0.0]

Unit

eV

Description

List of frequencies of incident light, the perturbing field, at which the time-dependent properties will be calculated.

GXCALPHA
Type

Float

Description

HyperPol
Type

Float

Default value

0.0

Unit

Hartree

Description

IFILES
Type

Integer

Default value

0

Description

Integration run including external files. Used for Van der Waals dispersion coefficients calculations.

IPRESP
Type

Integer

Default value

1

Description

IReal
Type

Integer

Default value

1

Description

KSORBRUN
Type

Bool

Description

MAGNETICPERT
Type

Bool

Description

MAXWAALS
Type

Integer

Default value

8

Description

NCycMx
Type

Integer

Default value

30

Description

NOFXCDR
Type

Bool

Description

NUMERIC
Type

Bool

Description

OPTICALROTATION
Type

Bool

Description

Octupole
Type

Bool

Description

Quadrupole
Type

Bool

Description

Raman
Type

Bool

Description

STARTREALGR
Type

Bool

Description

SYMRUN
Type

Bool

Description

Temperature
Type

Float

Default value

300.0

Unit

Kelvin

Description

Wavelength of incoming light is equal to the wavelength at which the calculation is performed and temperature is equal to room temperature (300K) Total Raman band is default, not the Q-branch of diatomic. (Relevant for Raman scattering cross section)

VANDERWAALS
Type

Integer

Description

VERDET
Type

Float

Default value

0.01

Description

For numerical differentiation d alfa(omega) /d omega, needed for Verdet constant, the default frequencies are omega + dverdt and omega - dverdt

ResponseFormalism
Type

Multiple Choice

Default value

Auto

Options

[Auto, Response, AOResponse]

Description

Set to RESPONSE or AORESPONSE.

Restart
Type

Block

Description

Options for restarts

NoOrb
Type

Bool

Default value

No

GUI name

Ignore orbitals

Description

Do not use orbitals from the restart file

NoSCF
Type

Bool

Default value

No

GUI name

Ignore SCF fit coefficients

Description

Do not use any fit coefficients from the restart file as a first approximation to the (fitted) SCF density for the new calculation. Instead, the sum-of-fragments density will be used, as in a non-restart run. Note, typically noSCF should be used in combination with noORB.

NoSmear
Type

Bool

Default value

No

GUI name

Ignore smearing

Description

Do not use any electron smearing data from the restart file.

SpinFlip
Type

Integer List

GUI name

Spin flip on restart for

Description

Select the atoms for which the spin is to be flipped upon restart.

RESTOCC
Type

Bool

Default value

No

Description

RIHartreeFock
Type

Block

Description

DependencyCoreRange
Type

Float

Description

Basis functions may be given a core character based on the range. For now only active in Band and only if present in the input

DependencyThreshold
Type

Float

Default value

0.001

Description

To improve numerical stability, almost linearly-dependent combination of basis functions are removed from the Hartree-Fock exchange matrix. If you obtain unphysically large bond energy in an Hybrid calculation, or an unphysically low correlation energy in an RPA, MP2, or double hybrid calculation, you might try setting the DependencyThreshold to a larger value (e.g. 3.0E-3) Note, that in GW calculations and GW-BSE calculations the default for this key is 5.0e-3.

FitGenerationDetails
Type

Block

Description

Technical details about how the RI Hartree-Fock fit functions are generated.

BoostL
Type

Bool

Default value

No

Description

Add extra max(l)+1 diffuse function When l denotes the highest angular momentum present in the primary basis, FromBasisProducts will generate auxiliary fit functions with up to 2l angular momentum. When this key is set to true, the maximum angular momentum in the auxiliary fit set becomes 2l+2. Typically, this option is not needed and when precision issues arise, it is rather advised to adjust the OneCenterDependencyThreshold key to a smaller value.

LapackWorkAround
Type

Bool

Default value

No

Description

GetFitFunctionsForAtomType diagonalization done with Lapack instead of Scalapack

Method
Type

Multiple Choice

Default value

Auto

Options

[Auto, FromBasisProducts]

Description

The way in which fit functions are generated. The main distinction is whether it depends on the basis functions used. When FromBasisProducts is used, the auxiliary basis is generated directly from the products of primary basis functions. This has the advantage that the auxiliary fit adapts automatcally to the basis set size. Especially for basis sets of QZ quality or larger, this is often necessary to otbain highly precise correlation energies using RPA or double hybrids FromBasisProducts option is also useful for GW or BSE calculations with basis sets of QZ quality or larger.

OneCenterDependencyThreshold
Type

Float

Default value

1e-08

Description

This key is only active when FromBasisProducts is chosen as method to generate the auxiliary basis. This threshold controls the size, and at the samw time, the precision of the auxiliary basis set. A smaller number leads to a larger auxiliary fit set. The default value of 1e-8 is typically sufficient to converge correlation energies and QP energies to a very high precision. It corresponds to an auxiliary basis which is typically 8-9 times larger than the primary basis.

UseBandRadialGrid
Type

Bool

Default value

Yes

Description

Only applies to band. The band logarithmic grid ranges (by default) from 1e-6 to 100 with 3000 points. Otherwise 300 points will be used. For 0-periodicity (molecules) it is advaisable to set this key to false since lots of memory is needed to evaluate all necessary integrals.

FitSetQuality
Type

Multiple Choice

Default value

Auto

Options

[Auto, VeryBasic, Basic, Normal, Good, VeryGood, Excellent, FromBasisProducts]

Description

The quality of auxiliary fit set employed in the RI scheme. If ‘Auto’, the value of the RIHartreeFock Quality option will be used. Normal quality is generally sufficient for basis sets up to and including TZ2P. For larger basis sets (or for benchmarking purposes) a VeryGood fit set is recommended. Note that the FitSetQuality heavily influences the computational cost of the calculation.

IntegrationQuality
Type

Multiple Choice

Options

[VeryBasic, Basic, Normal, Good, VeryGood, Excellent]

Description

Quality of the numerical integration for evaluating the integrals between basis functions and fit functions. If IntegrationQuality is not defined in input, the value defined in RIHartreeFock%Quality will be used.

Quality
Type

Multiple Choice

Default value

Auto

Options

[Auto, VeryBasic, Basic, Normal, Good, VeryGood, Excellent]

Description

Numerical accuracy of the RI procedure. If ‘Auto’, the quality specified in the ‘NumericalQuality’ will be used.

QualityPerRegion
Type

Block

Recurring

True

Description

Sets the fit-set quality for all atoms in a region. If specified, this overwrites the globally set quality.

Quality
Type

Multiple Choice

Options

[VeryBasic, Basic, Normal, Good, VeryGood, Excellent]

Description

This region’s quality of the auxiliary fit set employed in the RI scheme.

Region
Type

String

Description

The identifier of the region for which to set the quality.

ResponseQuality
Type

Multiple Choice

Options

[VeryBasic, Basic, Normal, Good, VeryGood, Excellent]

Description

Numerical accuracy of the RI procedure for the Response module.

ThresholdQuality
Type

Multiple Choice

Options

[VeryBasic, Basic, Normal, Good, VeryGood, Excellent]

Description

Linear scaling thresholds (also used for determining at what range the multiple approximation is used). To disable all linear scaling thresholds set this to Excellent.

UseMe
Type

Bool

Default value

Yes

Description

Set to False if you want to use the old RI scheme (ADF only)

RISM
Type

Non-standard block

Description

3D-RISM-related input keys.

Save
Type

String

Recurring

True

Description

A sequence of file names separated by blanks or commas. Possible file names are TAPE10, TAPE13, TAPE14.

scaledkinfunctionals
Type

Bool

Default value

No

Description

FDE option.

SCF
Type

Block

Description

Control aspects of the Self Consistent Field procedure

AccelerationMethod
Type

Multiple Choice

Default value

ADIIS

Options

[ADIIS, fDIIS, LISTb, LISTf, LISTi, MESA, SDIIS]

Description

SCF acceleration method. The default method is ADIIS, which is actually a mix of A-DIIS and SDIIS: A-DIIS is used at the start of the SCF and SDIIS is used closer to convergence, with a smooth switching function. The other methods are from the LIST family developed by Alex Wang and co-workers. They may perform better than the default in some situations. Setting AccelerationMethod to SDIIS effectively disables A-DIIS and is equivalent to the legacy mixing+DIIS method.

Converge
Type

Float List

Default value

[1e-06, 0.001]

Description

The criterion to stop the SCF updates. The tested error is the commutator of the Fock matrix and the P-matrix (=density matrix in the representation of the basis functions) from which the F-matrix was obtained. This commutator is zero when absolute self-consistency is reached. Convergence is considered reached when the maximum element falls below SCFcnv and the norm of the matrix below 10*SCFcnv. The default is fairly strict. A second criterion which plays a role when the SCF procedure has difficulty converging. When in any SCF procedure the currently applicable criterion does not seem to be achievable, the program stops the SCF. When the secondary criterion (sconv2) has been met, only a warning is issued and the program continues normally.

DIIS
Type

Block

Description

The maximum number of SCF cycles allowed.

BFac
Type

Float

Default value

0.0

GUI name

Bias DIIS towards latest vector with

Description

By default, the latest vector is not favored in the DIIS algorithm (value 0.0). A sensible value would be 0.2.

CX
Type

Float

Default value

5.0

GUI name

Reduce DIIS space when coefs >

Description

The DIIS space is reduced when very large DIIS coefficients appear. The value is the threshold.

CXX
Type

Float

Default value

25.0

GUI name

No DIIS (but damping) when coefs >

Description

When very large DIIS coefficients appear, switch to traditional damping. The value is the threshold.

Cyc
Type

Integer

Default value

5

GUI name

Start DIIS anyway at cycle

Description

When A-DIIS is disabled, the Pulay DIIS will start at this iteration irrespective of the DIIS OK value.

N
Type

Integer

Default value

10

GUI name

Size of DIIS space

Description

The number of expansion vectors used for accelerating the SCF. The number of previous cycles taken into the linear combination is then n-1 (the new computed potential is also involved in the linear combination)

Ok
Type

Float

Default value

0.5

GUI name

Start DIIS when max [F,P] <

Description

The Pulay DIIS starting criterion, when A-DIIS is disabled,

Iterations
Type

Integer

Default value

300

GUI name

Maximum number of SCF cycles

Description

The maximum number of SCF cycles allowed.

LShift
Type

Float

Default value

0.0

Unit

Hartree

GUI name

Level shift

Description

The level shifting parameter. The diagonal elements of the Fock matrix, in the representation of the orbitals of the previous iteration, are raised by vshift hartree energy units for the virtual orbitals. This may help to solve convergence problems when during the SCF iterations charge is sloshing back and forth between different orbitals that are close in energy and all located around the Fermi level. Level shifting is not supported in the case of Spin-Orbit coupling. At the moment properties that use virtuals, like excitation energies, response properties, NMR calculations, will give incorrect results if level shifting is applied.

LShift_cyc
Type

Integer

Default value

1

Description

Specifies that level shifting is not turned on before the given SCF cycle number (for the start-up geometry).

LShift_err
Type

Float

Default value

0.0

Description

Specifies that level shifting will be turned off by the program as soon as the SCF error drops below a threshold.

MESA
Type

String

Description

Mixing
Type

Float

Default value

0.2

GUI name

Mixing (% new vector included)

Description

When none of the SCF acceleration methods is active, the next Fock matrix is determined F = mixing * F_n + (1-mixing)F_(n-1).

Mixing1
Type

Float

Default value

0.2

GUI name

Mixing 1st SCF cycle

Description

The mixing parameter at the 1st SCF cycle.

OldSCF
Type

Bool

Default value

No

Description

Disable the default SCF algorithm and use the old SCF algorithm. The default SCF improves performance for big systems on big machines (when your calculation uses many tasks). It is also recommended for machines with slow disk I/O as it writes less data to disk. The default convergence method supported is A-DIIS, but LISTi is also supported.

ROSCF
Type

Block

Description

Settings for the ROSCF method.

Alpha
Type

Float List

Default value

[0.5, 0.5, 0.5]

Description

Coefficients to build the alpha-spin orbital contribution to the diagonal closed-, open-, and virtual-shell blocks of the Fock matrix. The beta-spin orbital contributions are 1.0 minus the alpha ones.

SCRF
Type

Non-standard block

Description

Input for SCRF.

SelectExcitation
Type

Block

Description

DipStrength
Type

Float

Description

GRIMMEAEX
Type

Float

Description

GRIMMEALPHA
Type

Float

Description

GRIMMEBETA
Type

Float

Description

GRIMMEDEMAX
Type

Float

Description

GRIMMEPERTC
Type

Bool

Description

GRIMMETPMIN
Type

Float

Description

HighExcit
Type

Float

Description

NOGRIMMEPERTC
Type

Bool

Description

NOverlap
Type

Integer

Default value

0

Description

OscStrength
Type

Float

Description

Use only pairs of an occupied and virtual orbital as guess vectors, for which the oscillator strength of the single-orbital transition is larger than this value

SetLargeEnergy
Type

Float

Default value

1000000.0

Unit

Hartree

Description

The orbital energies of the uninteresting occupied orbitals are changed to -epsbig Hartree, and the orbital energies of the uninteresting virtual orbitals are changed to epsbig Hartree

SetOccEnergy
Type

Float

Description

All occupied orbitals that have to be used will change their orbital energy to this value. In practice only useful if one has selected one occupied orbital energy, and one want to change this to another value. Default: the orbital energies of the occupied orbitals that are used are not changed.

UseOccRange
Type

Float List

Unit

Hartree

Description

Use only occupied orbitals which have orbital energies between the two numbers.

UseOccVirtNumbers
Type

Integer List

Description

Use only pairs of an occupied and virtual orbital as guess vectors, for which in the sorted list of the orbital energy differences, the number of the single-orbital transition is between the two numbers.

UseOccVirtRange
Type

Float List

Unit

Hartree

Description

Use only pairs of an occupied and virtual orbital, for which the orbital energy difference is between the two numbers

UseOccupied
Type

Non-standard block

Description

Use only the occupied orbitals which are specified

UseScaledZORA
Type

Bool

Default value

No

Description

Use everywhere the scaled ZORA orbital energies instead of the ZORA orbital energies in the TDDFT equations. This can improve deep core excitation energies. Only valid if ZORA is used.

UseVirtRange
Type

Float List

Unit

Hartree

Description

Use only virtual orbitals which have orbital energies between the two numbers

UseVirtual
Type

Non-standard block

Description

Use only the virtual orbitals which are specified

SFTDDFT
Type

Bool

Default value

No

GUI name

Spin-flip excitations

Description

Calculate spin-flip excitation energies (requires TDA and FORCEALDA keys).

SharcOverlap
Type

Bool

Default value

No

Description

Skip
Type

String

Recurring

True

Description

Expert key. To restrict which parts of the program are actually executed.

SlaterDeterminants
Type

Non-standard block

Description

The calculation of the one-determinant states based on the AOC reference state is controlled with this key.

Solvation
Type

Block

Description

ARO
Type

Float

Description

Acid
Type

Float

Description

Ass
Type

Bool

Description

Base
Type

Float

Description

BornC
Type

Float

Description

Coulomb constant for Born

C-Mat
Type

String

Description

COSKFAtoms
Type

Integer List

Recurring

True

Description

This subkey COSKFATOMS specifies for which nuclei the segments in the COSMO section of the COSKF file should be used. Default all nuclei should be used, i.e. as for omitting the subkey COSKFATOMS. The numbers refer to the input ordering in the ADF calculation.

Charged
Type

String

Description

Chgal
Type

Float

Description

CsmRsp
Type

Bool

Description

Cust
Type

String

Description

Debug
Type

String

Description

Disc
Type

String

Description

Div
Type

String

Description

EPS
Type

Float

Description

ForceCosmo
Type

String

Description

HALO
Type

Float

Description

Lpr
Type

Bool

Description

NoAss
Type

Bool

Description

NoCsmRsp
Type

Bool

Description

NoLpr
Type

Bool

Description

NoPVec
Type

Bool

Description

PVec
Type

Bool

Description

PrintSM12
Type

Bool

Description

RADII
Type

Non-standard block

Description

RadSolv
Type

Float

Description

Ref
Type

Float

Description

SCF
Type

String

Description

Solv
Type

String

Description

Solvent details

Surf
Type

Multiple Choice

Default value

delley

Options

[wsurf, asurf, esurf, klamt, delley, wsurf nokeep, asurf nokeep, esurf nokeep, klamt nokeep, delley nokeep]

Description

Defines the type of cavity to be used.

Tens
Type

Float

Description

SOMCD
Type

Bool

Default value

No

Description

MCD option. Required for a calculation of MCD temperature-dependent C terms. The calculation must be an unrestricted and scalar relativistic ZORA.

SOPert
Type

Block

Description

Key for perturbative inclusion of spin-orbit coupling.

EShift
Type

Float

Default value

0.2

Description

The actually calculated eigenvalues are calculated up to the maximum singlet-singlet or singlet-triplet scalar relativistic excitation energy plus eshift (in Hartree).

GSCorr
Type

Bool

Default value

Yes

GUI name

Include GS

Description

The singlet ground state is included, which means that spin-orbit coupling can also have some effect on energy of the ground state. The spin-orbit matrix in this case is on basis of the ground state and the singlet and triplet excited states.

NCalc
Type

Integer

Description

Number of spin-orbit coupled excitation energies to be calculated. Default (and maximum) value: 4 times the number of scalar relativistic singlet-singlet excitations.

sozero
Type

Bool

Default value

No

Description

Debug option to set spin-orbit matrix to zero.

SpinPolarization
Type

Float

Description

The spin polarization of the system, which is the number of spin-alpha electrons in excess of spin-beta electrons. Specification is only meaningful in a spin-unrestricted calculation. However, specification is not meaningful in an unrestricted Spin-Orbit coupled calculation using the (non-)collinear approximation.

STContrib
Type

Bool

Default value

No

Description

For an analysis of spin-orbit coupled excitations in terms of scalar relativistic singlet and triplet excitations. In order to get this analysis one needs to perform a scalar relativistic TDDFT calculation of excitation energies on the closed shell molecule first, and use the resulting adf.rkf as a fragment in the spin-orbit coupled TDDFT calculation of excitation energies, including this keyword STCONTRIB.

STOFit
Type

Bool

Default value

No

Description

Computation of the Coulomb potential with the pair fit method.

StopAfter
Type

String

Description

SubExci
Type

Block

Description

Subsystem TDDFT (FDE)

CICoupl
Type

Bool

Default value

No

Description

Within the Tamm-Dancoff Approximation, the couplings between localized excited states on different subsystems correspond directly to so-called exciton couplings. The CICOUPL keyword, in conjunction with TDA, prints these exciton couplings. It is also possible to use CICOUPL with full FDEc-TDDFT. In that case, the excitonic couplings between monomers are reconstructed from an effective 2x2 CIS-like eigenvalue problem.

COULKERNEL
Type

Bool

Default value

Yes

Description

COUPLBLOCK
Type

Bool

Default value

No

Description

COUPLSYS
Type

Integer List

Description

CPLTAPE
Type

String

Description

CThres
Type

Float

Default value

30.0

Unit

eV

Description

all excitations of all subsystems (present on the fragment TAPE21 files) with an excitation energy that differs by less than coupling_threshold. From one of the reference states are selected to be included in the coupling. Note that additional excited states of system 1 may be included here.

DIPVEL
Type

Bool

Default value

No

Description

DiagType
Type

Multiple Choice

Default value

EXACT

Options

[EXACT]

Description

EIGPRINT
Type

Integer

Default value

100

Description

ETHRES
Type

Float

Default value

0.0

Unit

eV

Description

Threshold for effective coupling

FULLGRID
Type

Bool

Default value

No

Description

InvGuess
Type

Multiple Choice

Default value

EigVal-OrbDiff

Options

[EigVal-OrbDiff, OrbDiff-OrbDiff, Exact]

Description

Type of states to be coupled

LOCALFXCK
Type

Bool

Default value

No

Description

Lowest
Type

Integer

Default value

10

Description

The selection of the excited states to be coupled consists of two steps

NITER
Type

Integer

Default value

1

Description

NOINTERSOLV
Type

Bool

Default value

No

Description

NOSOLVCCHECK
Type

Bool

Default value

No

Description

ONEGRID
Type

Bool

Default value

No

Description

OptStates
Type

Integer List

Description

If the keyword OPTSTATES is given, only those excited states of the first subsystem are considered as reference states that are given in this list.

PFRAGOUT
Type

Bool

Default value

No

Description

PTHRES
Type

Float

Default value

1.0

Description

SETDIAG
Type

Float

Description

SFThres
Type

Float

Default value

1e-05

Description

To reduce the computational effort, it is possible to ignore the effect of orbital pairs with coefficients less than solutionfactor_threshold in the solution factors (TDDFT eigenvectors) of the underlying uncoupled calculation in the construction of the exact trial densities during the calculation of the coupling matrix elements. These orbital pair contributions are not ignored in the subsequent calculation of transition moments, oscillator, and rotational strengths.

SMARTGRID
Type

Bool

Default value

No

Description

Stat2CPL
Type

Multiple Choice

Default value

OnlyKnown

Options

[OnlyKnown]

Description

Type of states to be coupled

TCOMEGA
Type

Bool

Default value

No

Description

Transpose construction of Omega matrix

TDA
Type

Bool

Default value

No

Description

TDA specifies the use of the Tamm-Dancoff-Approximation (Tamm-Dancoff approximation) in the underlying uncoupled FDE-TDDFT calculations. Contrary to the full SUBEXCI-TDDFT variant, SUBEXCI-TDA allows for the usage of hybrid functionals in the underlying uncoupled FDE-TDDFT calculations.

TKINKERNEL
Type

Bool

Default value

Yes

Description

XCKERNEL
Type

Bool

Default value

Yes

Description

Symmetry
Type

Multiple Choice

Default value

AUTO

Options

[AUTO, NOSYM, ATOM, C(LIN), D(LIN), C(I), C(S), C(2), C(2V), C(3V), C(4V), C(5V), C(6V), C(7V), C(8V), C(2H), D(2), D(3), D(4), D(5), D(6), D(7), D(8), D(2D), D(3D), D(4D), D(5D), D(6D), D(7D), D(8D), D(2H), D(3H), D(4H), D(5H), D(6H), D(7H), D(8H), O(H), T(D)]

Description

Use (sub)symmetry with this Schoenflies symbol. Can only be used for molecules. Orientation should be correct for the (sub)symmetry. Coordinates must be symmetric within SymmetryTolerance.

SymmetryTolerance
Type

Float

Default value

1e-07

Description

Tolerance used to detect symmetry in the system. If symmetry Schoenflies symbol is specified, the coordinates must be symmetric within this tolerance.

Tails
Type

Block

Description

Obsolete option for linear scaling and distance effects. We recommend using the LinearScaling key instead.

Bas
Type

Float

Description

Parameter related to the threshold for the calculation of basis functions on a block of integration points. A higher value implies higher precision. The default depends on the Integration numerical quality.

Fit
Type

Float

Description

Parameter related to the threshold for the calculation of fit functions on a block of integration points. A higher value implies higher precision. The default depends on the Integration numerical quality.

TDA
Type

Bool

Default value

No

Description

Use the Tamm-Dancoff approximation (TDA) (requires the EXCITATION block key)

TDDFTSO
Type

Bool

Default value

No

Description

TIDegeneracyThreshold
Type

Float

Default value

0.1

Unit

eV

Description

If the orbital energy of the fragment MO is within this threshold with fragment HOMO or LUMO energy, then this fragment MO is included in the calculation of the transfer integrals. Relevant in case there is (near) degeneracy.

Title
Type

String

Default value

*** (NO TITLE) ***

Description

Title of the calculation.

TotalEnergy
Type

Bool

Default value

No

GUI name

Print: Total Energy

Description

Calculate the total energy. Normally only the bonding energy with respect to the fragments is calculated. The total energy will be less accurate then the bonding energy (about two decimal places), and is not compatible with some options. In most cases the total energy will not be needed.

TransferIntegrals
Type

Bool

Default value

No

GUI name

: Charge transfer integrals (for transport properties)

Description

Calculate the charge transfer integrals, spatial overlap integrals and site energies. Charge transfer integrals can be used in models that calculate transport properties.

Unrestricted
Type

Bool

Default value

No

Description

By default, a spin-restricted calculation is performed where the spin alpha and spin beta orbitals are spatially the same.

UnrestrictedFragments
Type

Bool

Default value

No

Description

Use fragments calculated a spin-unrestricted calculation: the spin alpha and spin beta orbitals may be spatially different. The total spin polarization of your fragments must match the spin polarization of your final molecule.

UseSPCode
Type

Bool

Default value

No

Description

Use Patchkovskii routines for PBE

VectorLength
Type

Integer

GUI name

Vectorlength (blocksize)

Description

Specify a different batch size for the integration points here (default: 128 on most machines and 2047 on vector machines).

VSCRF
Type

Non-standard block

Description

Input for VSCRF.

XC
Type

Block

Description

Definition of the XC.

Dispersion
Type

String

Description

Dispersion corrections.

DoubleHybrid
Type

String

Description

Specifies the double hybrid functional that should be used during the SCF.

EmpiricalScaling
Type

Multiple Choice

Default value

None

Options

[None, SOS, SCS, SCSMI]

Description

Calculate the (SOS/SCS/SCSMI)-MP2 correlation energy.

GCPparameters
Type

String

Description

Applying parameters for the geometrical counter poise correction.

GGA
Type

String

Description

Specifies the GGA part of the XC Functional

HartreeFock
Type

Bool

Default value

No

Description

Use the Hartree-Fock exchange should be used during the SCF.

Hybrid
Type

String

Description

Specifies the hybrid functional that should be used during the SCF.

LDA
Type

String

Description

Defines the LDA part of the XC functional

LibXC
Type

String

Description

Use the LibXC library with the specified functional.

MP2
Type

Bool

Default value

No

Description

Calculate the MP2 correlation energy after the HF SCF is completed.

MetaGGA
Type

String

Description

Specifies that a meta-GGA should be used during the SCF

MetaHybrid
Type

String

Description

Specifies the meta-hybrid functional that should be used during the SCF.

Model
Type

String

Description

Model potential to be used

NoLibXC
Type

Bool

Default value

No

Description

Prevent the usage of the LibXC library

OEP
Type

String

Description

Defines the optimized effective potential expanded into a set of the fit functions

RPA
Type

Multiple Choice

Default value

None

Options

[None, Direct, Sigma, SOSEX, SOSSX]

Description

Specifies that RPA is used an possibly also a post-RPA method. By default, RPA is not used.

RangeSep
Type

String

Description

Range separated hybrids parameters

XCFun
Type

Bool

Default value

No

Description

Use the XCFun library

gCP
Type

String

Description

Use the geometrical counter poise correction.

XES
Type

Block

Description

X-ray emission spectroscopy

AllXESMoments
Type

Bool

Default value

No

GUI name

Print: All XES Moments

Description

Print out all the individual transition moments used within the calculation of the total oscillator strength

AllXESQuadrupole
Type

Bool

Default value

No

GUI name

: All XES Quadrupole

Description

Print out the individual oscillator strength components to the total oscillator strength

CoreHole
Type

String

GUI name

Acceptor orbital

Description

selection of the acceptor orbital for the calculation of the emission oscillator strengths. For example ‘CoreHole A1 2’ calculates oscillator strengths to the orbital 2 in irrep A1. In AMSinput you may also use the notation 2A1 (so first the orbital number, next the symmetry)

Enabled
Type

Bool

Default value

No

GUI name

Calculate XES

Description

Calculate the X-ray emission energies to a core orbital. By default it calculates the emission to the first orbital in the first symmetry.

ZExact
Type

Bool

Default value

No

Description

Expert option in TDDFT excitations.

ZFS
Type

String

Description

Calculate the zero-field splitting (ZFS) of an open shell ground state. An unrestricted calculation is required and a spin larger than 1/2, and no no spatial degeneracy. Scalar relativistic ZORA is required.

ZlmFit
Type

Block

Description

Options for the density fitting scheme ‘ZlmFit’.

AllowBoost
Type

Bool

Default value

Yes

Description

Allow automatic atom-dependent tuning of maximum l of spherical harmonics expansion. Whether or not this boost is needed for a given atom is based on an heuristic estimate of how complex the density around that atom is.

DensityThreshold
Type

Float

Default value

1e-07

Description

Threshold below which the electron density is considered to be negligible.

GridAngOrder
Type

Integer

Default value

21

Description

GridRadialFactor
Type

Float

Default value

1.0

Description

PartitionFunThreshold
Type

Float

Default value

0.0

Description

PotentialThreshold
Type

Float

Default value

1e-07

Description

Pruning
Type

Bool

Default value

Yes

Description

Quality
Type

Multiple Choice

Default value

Auto

Options

[Auto, Basic, Normal, Good, VeryGood, Excellent]

Description

Quality of the density-fitting approximation. For a description of the various qualities and the associated numerical accuracy see reference. If ‘Auto’, the quality defined in the ‘NumericalQuality’ will be used.

QualityPerRegion
Type

Block

Recurring

True

Description

Sets the ZlmFit quality for all atoms in a region. If specified, this overwrites the globally set quality.

Quality
Type

Multiple Choice

Options

[Basic, Normal, Good, VeryGood, Excellent]

Description

The region’s quality of the ZlmFit.

Region
Type

String

Description

The identifier of the region for which to set the quality.

lExpansion
Type

Integer

Default value

4

Description

lMargin
Type

Integer

Default value

4

Description