dft
KohnSham density functional theory.
In the global context this command runs a DFT groundstate calculation on a system specified through the structure subcommand; in other contexts it can be used to specify a type of DFT calculation.
For example, a PBE calculation on the water molecule might be run using:
dft(
structure( molecule = water )
ao = '631G*'
xc = PBE
)
Here is an advanced example to calculate the frozen orbital approximation to the singlettriplet energy gap in stretched NO+ with PBE0
with a different HF exchange factor (note that this calculation strategy is not very reasonable but it shows reasonable usages of several keywords):
singlet := dft(
structure(
formula = NO
bond_length = 2 angstrom
charge = 1
)
ao = 'Def2TZVP'
df = 'Def2TZVPJFIT'
xc = PBE0
exchange_factor = 0.2 ! override HF exchange factor
dispersion = D3
ansatz = u ! do unrestricted in order to use the orbitals later
spin = 0 ! singlet; this is actually the default
diagonalize_l_z = true ! to avoid convergence problems due to degenerate orbitals
no_symmetry_breaking = true ! try to obtain a closedshell solution
)
dft(
structure(
formula = NO
bond_length = 2 angstrom
charge = 1
)
ao = 'Def2TZVP'
df = 'Def2TZVPJFIT'
xc = PBE0
exchange_factor = 0.2 ! override HF exchange factor
dispersion = D3
ansatz = u
spin = 2 ! triplet
load = singlet ! use orbitals from above
max_iter = 0 ! Keep the initial orbitals
no_fail = true ! Use the unconverged solution
)
Subcommands
 admm
 atomic_guess
 average
 constant_potential
 d3
 d3bj
 delta_scf
 field
 grid
 load_mos
 mp2
 point_charges
 save_mos
 solvation
 structure
Options
ansatz

SCF wavefunction ansatz.
 The type is string
 The default is default
 The value must be one of:
default
 default ansatz for given number of electronsr
 spinrestricted closedshell ansatzu
 spinunrestricted openshell ansatzro
 spinrestricted openshell ansatz. By default, the Davidson coupling scheme is used. See rohf_scheme for different choices of the coupling schemes.cu
constrained spinunrestricted openshell ansatz of Tsuchimochi and Scuseria.
This ansatz gives the same total energy and wavefunction as the restricted openshell ansatz ro, but exhibits more robust SCF convergence and gives physically meaningful orbital energies, i.e. satisfying Koopmans' theorem, and the aufbau principle.
Another difference between this ansatz and the ro ansatz is that it yields two different sets of spin orbitals, where as the ro ansatz gives only one set of orbitals for the alpha and beta spins.
However, one can obtain the ro orbitals from the cu wavefunction by setting ro_orbitals_from_cu to true. For example:
hf( structure( formula = OH bond_length = 1.0 angstrom ) ao = 'Def2SVP' ansatz = cu ro_orbitals_from_cu = true )
ao

Atomicorbital basis set name. No constraint is implied by the parser, but the basis set file must exist (in the directory basis within the data directory).
Adding pre or postfix of (s) will limit the maximum angular momentum to sfunctions. (sp) limits to s and pfunctions, and this works up to (spdfghi). The complete set of functions must be present i.e. (s[p[d[f[g[h[i]]]]]]).
Note: the input value must match exactly the name of the basis set file in the basis directory.
This option is mandatory.
 The type is stringlowered
 There is no default value.
ao_custom

Provide custom basis set for particular elements
 The type is {stringlowered}
 There is no default value.
ao_threshold

Threshold applied to prescreen AO shell pairs based on radial overlap estimate.
 The type is real
 The default is 1e12
 The value must be nonnegative
charge

Total molecular charge. No constraint is imposed, but clearly the value has to be such that for a given molecule the number of electrons is nonnegative, and that the number of electrons does not exceed the number that can be described with the given atomicorbital basis. Note that noninteger values are possible as well.
This option is deprecated. Please use the charge option inside structure instead.
This option is deprecated.
 The type is real
 There is no default value.
check_fock_norm

Check the norm of the Fock matrix against the numerical derivative of the energy before starting SCF. Only for debugging purposes.
 The type is bool
 The default is false
coulomb_factor

Factor for electronic Coulomb energy. By and large this should never be changed.
 The type is real
 The default is 1.0
coulomb_method

Method for computing the Coulomb contribution to Fock matrix and energy.
 The type is string
 The default is incore_df
 The value must be one of:
incore_df
Use conventional incore densityfitting to compute the Coulomb contribution to Fock matrix and energy.
This algorithm is fast but has a memory requirement of about \(8 * N_\text{ao}^2 * N_\text{df}\) Bytes, where \(N_\text{ao}\) and \(N_\text{df}\) are the number of AO and densityfitting basis functions, respectively. Therefore, it may not work for calculations on very large systems or with very large basis; in these cases, use
coulomb_method = direct_df
instead.direct_df
Use integraldirect densityfitting to compute the Coulomb contribution to Fock matrix and energy.
This algorithm has minimal memory requirement but is generally slower than the
incore_df
method. Use it whencoulomb_method = incore_df
does not work.This method also indicates use of integral screening (see schwarz_threshold) and incremental Fock build (see incremental_fock).
direct_4idx
Use integraldirect approach to compute the 4index electron repulsion integrals (ERIs).
Currently, this algorithm is very slow, and is recommended to be used only for testing purposes (on small systems with small basis).
coulomb_metric

Algorithm regarding the storage and use of Coulombmetric integrals in density fitting.
 The type is string
 The default is Cholesky
 The value must be one of:
Cholesky
 Use Cholesky decomposition of the twoindex Coulomb DF integrals and forward/backward substitution to compute DF Coulomb matrix and energy. This is the default algorithm.linear solver
 Solve the linear system equations for DF Coulomb every SCF step.inverse
 Use precomputed (pseudo)inverse of the twoindex DF integrals to compute DF Coulomb. This becomes numerically unstable when system or densityfitting basis is large, so use with caution.inverse sqrt
 Use precomputed inverse squareroot of the twoindex DF integrals to compute DF Coulomb. This requres pretransformation of 3index DF integrals.
df

Density fitting basis name. This basis is used to fit products of the form \( ij) \) where \( i \) and \( j \) are occupied molecular orbitals.
Note: the input value must match exactly the name of the basis set file in the basis directory.
 The type is stringlowered
 There is no default value.
df_custom

Provide custom density fitting basis set for particular elements
 The type is {stringlowered}
 There is no default value.
diagonalize_l_z

Switch whether for degenerate orbitals the l_z operator shall be diagonalized in order to obtain a unique set of orbitals. This is for example useful for linear molecules. If your calculation is on a single atom, use diagonalize_l_z_atom.
 The type is bool
 The default is false
diagonalize_l_z_atom

See diagonalize_l_z; in case of a single atom, this switch is used instead of diagonalize_l_z. For single atoms the default is to make use of the option.
 The type is bool
 The default is true
diis

Method of DIIS.
 The type is stringlowered
 The default is adiis+cdiis
 The value must be one of:
none
 DIIS is not used.cdiis
 This is the original DIIS algorithm by P. Pulay. P. Pulay, Chem. Phys. Lett. 73, 393 (1980).ediis
 Energybased DIIS which minimizes the HartreeFock energy functional. Kudin, Scuseria and Cances, J. Chem. Phys. 116, 8255 (2002).adiis
 DIIS based on the augmented RoothaanHall energy. X. Hu and W. Yang, J. Chem. Phys. 132, 054109 (2010).ediis+cdiis
 Combination of these two algorithms; see diis_switch_threshold_gradadiis+cdiis
 Combination of these two algorithms; see diis_switch_threshold_grad
diis_max

Maximum number of vectors for DIIS.
 The type is int
 The default is 10
 The value must be nonnegative
diis_shift

Diagonal shift for regularization of DIIS.
 The type is real
 The default is 0
 The value must be nonnegative
diis_switch_threshold_grad

In DIIS modes ADIIS+CDIIS and EDIIS+CDIIS the algorithm is switched to CDIIS if the gradient falls below this threshold.
 The type is real
 The default is 1e1
 The value must be nonnegative
dispersion

Add dispersion correction to energy
 The type is string
 There is no default value.
 The value must be one of:
none
 No dispersion correctionD3
 Use Grimme D3 zero damping dispersion correction
energy_threshold

SCF convergence threshold using the absolute value of the energy difference between iterations.
 The type is real
 The default is 1e6
 The value must be nonnegative
exchange_factor

Factor for exact exchange. The default value is 1.0 for HartreeFock, 0.0 for Hartree theory, and whatever the appropriate factor is for hybrid exchangecorrelation functionals. This option is overridden for range separated hybrid functionals.
 The type is real
 There is no default value.
exchange_method

Method for computing the exact exchange contribution to Fock matrix and energy.
 The type is string
 The default is pre_transformed_df
 The value must be one of:
incore_df
Use conventional incore densityfitting to compute the exchange contribution to Fock matrix and energy.
This algorithm is fast but has a memory requirement of about \(8 * N_\text{ao}^2 * N_\text{df}\) Bytes, where \(N_\text{ao}\) and \(N_\text{df}\) are the number of AO and densityfitting basis functions, respectively. Therefore, it may not work for calculations on very large systems or with very large basis; in these cases, use
coulomb_method = direct_df
instead.pre_transformed_df
Use the pretransformed densityfitting integrals to compute the exact exchange contribution to Fock matrix and energy.
This algorithm is faster than
incore_df
when SCF converges slowly (ca. with more than 10 SCF steps), and the speepup increases with the number of SCF steps; but is slower when SCF converges within a few steps.This algorithm has the same memory requirement as
incore_df
.occupied_df
Use the occRIK algorithm (incore version) to compute the exact exchange contribution to Fock matrix and energy.
This algorithm is ~ 2 times faster than
incore_df
for normal calculations (e.g. with doublezeta AO basis), and the speedup increases when larger basis is used.See this paper for a detailed description of the algorithm.
This algorithm has the same memory requirement as
incore_df
.semi_numeric
 Use seminumeric approach to compute the exact exchange contribution to Fock matrix and energy.direct_4idx
Use integraldirect approach to compute the 4index electron repulsion integrals (ERIs).
Currently, this algorithm is very slow, and is recommended to be used only for testing purposes (on small systems with small basis).
final_threshold

Final threshold for prescreening integrals during direct SCF. A shell block of integrals are computed only when the product of the integral estimate (based on CauchySchwarz inequality) and the largest density matrix element within the shell block is larger than this threshold. This is applied to later stage of SCF iterations.
 The type is real
 The default is 1e12
 The value must be nonnegative
fock_damping

Amount of previous Fock matrix to use in Fock damping. The new Fock matrix for iteration \( n \): \( F_{n} = (1\alpha) F_{n} + \alpha F_{n1} \) where \( \alpha \) is the fock_damping_factor.
 The type is real
 The default is 0.7
fock_damping

Amount of previous Fock matrix to use in Fock damping. The new Fock matrix for iteration \( n \): \( F_{n} = (1\alpha) F_{n} + \alpha F_{n1} \) where \( \alpha \) is the fock_damping_factor.
 The type is real
 The default is 0.7
fock_damping_gradient_threshold

If this keyword is specified, Fock matrix extrapolation is initially performed using a damping (see fock_damping). When the largest element of the absolute orbital gradient drops below fock_damping_gradient_threshold, DIIS will be used. If this keyword is absent, DIIS is used straight away.
 The type is real
 There is no default value.
fock_damping_gradient_threshold

If this keyword is specified, Fock matrix extrapolation is initially performed using a damping (see fock_damping). When the largest element of the absolute orbital gradient drops below fock_damping_gradient_threshold, DIIS will be used. If this keyword is absent, DIIS is used straight away.
 The type is real
 There is no default value.
frozen_grid

Use the frozengrid approximation when calculating geometrical derivatives.
 The type is bool
 The default is false
guess

Initial guess for the SCF wavefunction.
 The type is string
 The default is SAD
 The value must be one of:
SAD
 Superposition of Atomic Densities (SAD).H0
 Using eigenvectors of the core Hamiltonian as the initial guess. This is equivalent to setting the initial density to zero.
incremental_fock

Whether to use incremental Fock build for computing the Coulomb and exact exchange contributions to Fock matrix and energy.
By default, this is turned on for integral direct algorithms and off for incore algorithms. Explicitly setting this option will override the default behaviour.
 The type is bool
 There is no default value.
initial_threshold

Initial threshold for prescreening integrals during direct SCF. A shell block of integrals are computed only when the product of the integral estimate (based on CauchySchwarz inequality) and the largest density matrix element within the shell block is larger than this threshold. Only effective when incremental_fock is on. This is applied to earlier stage of SCF iterations. The threshold will be tightened to final_threshold when switching_threshold is satisfied.
 The type is real
 The default is 1e9
 The value must be nonnegative
level_shift

Turn on level shifting to improve SCF convergence. Raises the energy of virtual orbitals by level shifting value. Whether to remove the level shift at the end is controlled by option remove_level_shift.
 The type is real
 The default is 0
 The value must be nonnegative
load

Name of assigned result (containing orbitals) to start the SCF from.
 The type is string
 There is no default value.
max_incremental_fock_steps

Maximum number of steps of incremental Fock build before a full Fock build.
 The type is int
 The default is 20
 The value must be positive
max_iter

Maximum number of SCF iterations.
 The type is int
 The default is 128
 The value must be nonnegative
mom

Switch whether the maximum overlap method (MOM) will be used. This strategy improves convergence of nonaufbau occupations. CAUTION: Once mom is activated, the occupation numbers are fixed. A calculation with, for example, temperature may not work as intended in combination with mom.
 The type is bool
 The default is false
mom_activation_threshold

If MOM is used, an initial occupation first needs to be established before it can be kept. If this threshold is set to a nonzero value, MOM will be switched on once the electronic gradient falls below this threshold, keeping the occupation obtained at that iteration. The special value 0 indicates that MOM keeps the initial occupation (from the first cycle).
 The type is real
 The default is 0.0
multiplicity

Spin multiplicity \(2S + 1\)  only valid for integerelectron calculations. For nonintegerelectron number, or for higher multiplcities, use the spin option.
By default entos selects the lowest available spin multiplicity.
 The type is string
 There is no default value.
 The value must be one of:
singlet
 2S + 1 = 1; S = 0doublet
 2S + 1 = 2; S = 1/2triplet
 2S + 1 = 3; S = 1quartet
 2S + 1 = 4; S = 3/2quintet
 2S + 1 = 5; S = 2sextet
 2S + 1 = 6; S = 5/2
name

Specify the name of a set of results.
This option is deprecated.
 The type is string
 There is no default value.
name

Specify the name of a set of results.
This option is deprecated.
 The type is string
 There is no default value.
no_fail

If set to true, the program will continue its execution even if the SCF does not converge. This is useful for frozenorbital calculations.
 The type is bool
 The default is false
no_symmetry_breaking

In case of a unrestricted singlet calculation, in the first cycle half of the electron(s) in the alpha HOMO is shifted to the LUMO, unless this flag is set to true or the SCF starts from previous orbitals.
 The type is bool
 The default is false
number_type

Number type for orbitals and operators, whether real or complex.
 The type is string
 The default is real
 The value must be one of:
real
 Use real numbers for orbital coefficents and fock matrices.complex
 Use complex numbers for orbitals coefficents and fock matrices.
orbital_grad_threshold

SCF convergence threshold using the infinity norm of the orbital gradient.
 The type is real
 The default is 1e5
 The value must be nonnegative
orthogonalization

Method to orthogonalize the atomic orbital basis. Note that in case of a nearly linearly dependent basis (see overlap_threshold) the canonical algorithm is used irrespective of this option.
 The type is stringlowered
 The default is symmetric
 The value must be one of:
symmetric
 Symmetric orthogonalization of the AO basis. Uses the symmetric inverse square root of the overlap matrix for the orthogonalization.canonical
 Canonical orthogonalization of the AO basis.cholesky
 Orthogonalization through Cholesky decomposition of the overlap matrix.
overlap_threshold

Threshold for throwing away the smallest eigenvalues of the overlap matrix. This is a safety measure for calculations with nearlinearly dependent basis sets. Usually, the default value should be fine.
 The type is real
 The default is 1e7
 The value must be nonnegative
pairwise_potential

Specify the pairwise potential.
 The type is string
 There is no default value.
print_level

Print level.
 The type is int
 There is no default value.
 The value must be one of:
2
 No output1
 Minimum output0
 Output that doesn't scale with system size1
 Output that scales linearly with system size2
 (Debugging) output that scales quadratically with system size3
 (Debugging) output that scales cubically with system size
pseudo_diagonalization

Whether to use pseudodiagonalization instead of full diagonalization of the Fock matrix. Recommended for calculations on very large systems or with a very large basis.
 The type is bool
 The default is false
radial_threshold

Threshold for radial density cutoff, used in screening in the evaluation of exchangecorrelation functionals.
 The type is real
 The default is 1e6
remove_level_shift

Remove level shift from final orbitals.
 The type is bool
 The default is true
ro_orbitals_from_cu

Whether to constuct ROHF/ROKS orbitals and orbital energies from a converged CUHF/CUKS wavefunction.
 The type is bool
 The default is true
rohf_scheme

The coupling scheme for constructing the ROHF effective Fock matrix. Note that different choices give the same SCF total energy, but they give different sets of orbitals and orbital energies. See Plakhutin, Gorelik, and Breslavskaya, J. Chem. Phys. 125, 204110 (2006) for a comprehensive discussion on different coupling schemes.
 The type is stringlowered
 The default is davidson
 The value must be one of:
mcweeny_diercksen
 Use the couping scheme of McWeeny and Diercksen. See McWeeny and Diercksen, J. Chem. Phys. 49, 4852 (1968)davidson
 Use the couping scheme of Davidson. See Davidson, Chem. Phys. Lett. 21, 565 (1973)
schwarz_threshold

Threshold applied to CauchySchwarz integral screening.
 The type is real
 The default is 1e10
 The value must be nonnegative
scramble_complex

Add noise to the imaginary part of the guess density while keeping it hermitian. This option is only used if number_type = complex.
 The type is bool
 The default is true
scramble_complex_density_only

Scramble only the initial density (leaving the orbitals unchanged) in complex orbital calculations. Use scramble_complex to scramble the density and orbitals.
The change in the guess density implies a change in the guess orbitals and/or occupation numbers which are needed for orbitaldependent potentials. To obtain the adapted orbitals and occupations, the density must be diagonalized, which may be expensive. Usually, most parts of the potential are calculated directly from the density and scrambling in these parts is sufficient to break the symmetry. Thus, one may be able to achieve symmetrybreaking even when the orbitals and occupations are left unchanged.
 The type is bool
 The default is false
scramble_parameter

The amount of noise that is added to the imaginary part of the guess density. This option is only relevant if scramble_complex is true.
 The type is real
 The default is 1e5
sparse_density_fitting

Whether to use the sparse form of the density fitting integrals for incore density fitting. The sparsity can be controlled with ao_threshold.
 The type is bool
 The default is false
spin

For spinunrestricted calculations: spin is \(2S\), where S is the total spin angular momentum
Notice that the value of this option need not be an integer. See the documentation on
spin_z
for an explanation.By default entos selects the lowest available spin multiplicity.
 The type is real
 There is no default value.
 The value must be nonnegative
spin_z

For spinunrestricted calculations, \(2m_s\), the number of alphaspin electrons minus the number of betaspin electrons.
If omitted,
spin_z
defaults to be the same as the total spin angular momentum.Notice that the value of this option need not be an integer, and need not be the same as the value of
spin
. See this paper for an explanation of noninteger charge.The thinking is similar to thinking about noninteger charge. A fractionalcharge (fc) density matrix is a mixed state of the density matrices of two Slater determinants (each with integer charge)
\[ \rho_\text{fc}(N+1/2) = \rho(N)/2 + \rho(N+1)/2 . \]A fractionalspin (fs) density matrix is a mixed state of two density matrices with different numbers of alpha and beta electrons
\[ \rho_\text{fs}(S=S, m_s=0) = \rho(N_\alpha = N_\text{el}/2 + S, N_\beta = N_\text{el}/2  S )/2 + \rho(N_\alpha = N_\text{el}/2  S, N_\beta = N_\text{el}/2 + S )/2 . \] The type is real
 There is no default value.
switching_threshold

This threshold controls switching between initial_threshold and final_threshold during an integraldirect SCF calculation. It is applied to the rootmeansquare of the change in density matrix elements between two consecutive SCF iterations.
 The type is real
 The default is 1e4
 The value must be nonnegative
temperature

Specify the temperature for the electrons and perform the SCF calculation in the canonicalensemble. Convergence is often poor with the default convergence settings, and using the original Pulay DIIS method is recommended (see diis option).
 The type is quantity
 The default is 0 kelvin
xc

Exchangecorrelation functional name. No constraint is implied by the parser, but the functional must exist within the program.
HartreeFock theory can be run by specifying
xc = HF
.Combinations of functionals can be produced using xc_mix.
 The type is stringlowered
 The default is none
 The value must be one of:
none
 No XC functional specified. Causes an error.HF
 100% exact exchange, i.e. HartreeFock theoryHartree
 No exchangecorrelation, i.e. Hartree theorySVWN
 Local density approximation (SLATER + VWN)LDA
 Local density approximation (SLATER + VWN)BLYP
 Combination of B88 and LYPBLYPD3
 Combination of B88 and LYP and D3 dispersion correctionBPW91
 Combination of B88 and PW91B3LYP
 B3LYP with VWN5 functionalB3LYPD3
 B3LYP with VWN5 functional and D3 dispersion correctionB3LYP3
 B3LYP with VWN3 functional (as implemented in Gaussian)B3LYP3D3
 B3LYP with VWN3 functional (as implemented in Gaussian) and D3 dispersion correctionB3LYP5
 B3LYP with VWN5 functionalPBE
 Perdew, Burke, Ernzerhof exchangecorrelation (PBEX + PBEC)PBED3
 Perdew, Burke, Ernzerhof exchangecorrelation (PBEX + PBEC) and D3 dispersion correctionPBE0
 PBE hybrid exchangecorrelationPBE0D3
 PBE hybrid exchangecorrelation and D3 dispersion correctionB973c
 B973c from Brandenburg, Bannwarth, Hansen and Grimme doi: 10.1063/1.5012601.This lowcost GGA method was parameterized to use the mTZVP basis, and selecting this functional automatically sets thedft(structure(molecule = water) xc = 'B973c' ao = mTZVP grid(neese = 5) )
ao = mTZVP
. It was also parameterized using a large quadrature grid, and the recommended grid isgrid(neese = 5)
.wB97X
 Chai and HeadGordon longrange corrected hybrid density functionalwB97XD3
 Lin, Li, Mao and Chai longrange corrected hybrid density functional and D3 dispersion correctionCAMB3LYP
 Cambridge screened hybridCAMB3LYPD3
 Cambridge screened hybrid and D3 dispersion correctionB88
 Becke 1988 exchangeDIRAC
 SlaterDirac exchangeLYP
 Lee, Yang, Parr correlationP86
 Perdew 1986 correlationPBE1PBE
 PBE hybrid exchangecorrelation. Note: this is synonymous with the betterknown PBE0 functionalPBE1PBED3
 PBE hybrid exchangecorrelation and D3 dispersion correction. Note: this is synonymous with the betterknown PBE0 functionalPBEC
 Perdew, Burke, Ernzerhof correlationPBER
 Perdew, Burke, Ernzerhof revised exchangecorrelation (PBERX + PBEC). Also known as revPBEPBERD3
 Perdew, Burke, Ernzerhof revised exchangecorrelation (PBERX + PBEC) and D3 dispersion correction. Also known as revPBEPBEX
 Perdew, Burke, Ernzerhof exchangePBERX
 Perdew, Burke, Ernzerhof exchange (revised)PW91
 Perdew, Wang 1991 correlationSLATER
 SlaterDirac exchangeVWN
 Vosko, Wilk, Nussair (5)VWN1
 Vosko, Wilk, Nussair (1)VWN5
 Vosko, Wilk, Nussair (5)XCHBLYPUW12
 Original XCHBLYPUW12 hybrid functionalBLYPOSUW12
 Oppositespin BLYPosUW12 hybrid functionalFBLYPOSUW12
 Oppositespin fBLYPosUW12 hybrid functional with 75% exact exchangeBLYPOSUW12D3BJ
 Oppositespin dispersionoptimised BLYPosUW12D3BJ hybrid functionalXCHBLYPUW12D3BJ
 Dispersioncorrected XCHBLYPUW12D3BJ hybrid functional
xc_mix

Exchangecorrelation functional given as a mixture of ingredients. Each list element should be a tuple with
[factor, functional]
; for example:xc_mix = [[0.15, LDA], [2.3e4, B3LYP]]
 The type is [(real, stringlowered)]
 There is no default value.