# 5.7.4 Tkatchenko-Scheffler van der Waals Model (TS-vdW)

(May 16, 2021)

Tkatchenko and Scheffler have developed a pairwise method for van der Waals (vdW, i.e., dispersion) interactions, based on a scaling approach that yields in situ atomic polarizabilities ($\alpha$), dispersion coefficients ($C_{6}$), and vdW radii ($R_{\text{vdW}}$) that reflect the local electronic environment. These are based on scaling the free-atom values of these parameters in order to account for how the volume of a given atom is modified by its molecular environment. The size of an atom in a molecule is determined using the Hirshfeld partition of the electron density. (Hirshfeld or “stockholder” partitioning, which also affords one measure of atomic charges in a molecule, is described in Section 10.2.1). In the resulting “TS-vdW” approach, only a single empirical range-separation parameter ($s_{R}$) is required, which depends upon the underlying exchange-correlation functional.

Note:  The parameter $s_{R}$ is currently implemented only for the PBE, PBE0, BLYP, B3LYP, revPBE, M06L, and M06 functionals.

The TS-vdW energy expression is based on a pairwise-additive model for the dispersion energy,

 $E_{\text{vdW}}^{\text{TS}}=-\frac{1}{2}\sum^{\text{atoms}}_{A}\sum^{\text{A}}_% {B\neq A}\left(\frac{C_{6,AB}^{\text{eff}}}{R_{AB}^{6}}\right)f_{\text{damp}}(% R_{AB})\;.$ (5.44)

As in DFT-D the $R^{-6}$ potentials in Eq. (5.44) must be damped at short range, and the TS-vdW model uses the damping function

 $f_{\text{damp}}(R_{AB})=\frac{1}{1+\exp\bigl{[}-d(R_{AB}/s_{R}R_{\mathrm{vdW,}% AB}^{\text{eff}}-1)\bigr{]}}$ (5.45)

with $d=20$ and an empirical parameter $s_{R}$ that is optimized in a functional-specific way to reproduce intermolecular interaction energies. Optimized values for several different functionals are listed in Table 5.4.

The pairwise coefficients $C_{6,AB}^{\text{eff}}$ in Eq. (5.44) are constructed from the corresponding atomic parameters $C_{6,A}^{\text{eff}}$ via

 $C_{6,AB}^{\text{eff}}=\frac{2C_{6,A}^{\text{eff}}C_{6,B}^{\text{eff}}}{\bigl{(% }\alpha_{B}^{\text{0,eff}}/\alpha_{A}^{\text{0,eff}}\bigr{)}\,C_{6,A}^{\text{% eff}}+\bigl{(}\alpha_{A}^{\text{0,eff}}/\alpha_{B}^{\text{0,eff}}\bigr{)}\,C_{% 6,B}^{\text{eff}}}\;,$ (5.46)

as opposed to the simple geometric mean that is used for $C_{6,AB}$ parameters in the empirical DFT-D methods [Eq. (5.25)]. These are “effective” $C_{6}$ coefficients in the sense that they account for the local electronic environment. As indicated above, this is accomplished by scaling the corresponding free-atom values, i.e.,

 $C_{6,A}^{\text{eff}}=C_{6,A}^{\text{free}}\left(\frac{V_{A,\text{eff}}}{V_{A,% \text{free}}}\right)^{\!2}$ (5.47)

where $V_{A,\text{eff}}$ is the effective volume of atom $A$ in the molecule, as determined using Hirshfeld partitioning. Effective atomic polarizabilities and vdW radii are obtained analogously:

 $\alpha^{\text{0,eff}}_{A}=\alpha_{A}^{\text{0,free}}\left(\frac{V_{A,\text{eff% }}}{V_{A,\text{free}}}\right)$ (5.48)
 $R_{\text{vdW,}A}^{\text{eff}}=R_{\text{vdW,}A}^{\text{free}}\left(\frac{V_{A,% \text{eff}}}{V_{A,\text{free}}}\right)^{\!1/3}\;.$ (5.49)

All three of these atom-specific parameters are therefore functionals of the electron density.

As with DFT-D, the cost to evaluate the dispersion correction in Eq. (5.44) is essentially zero in comparison to the cost of a DFT calculation. A recent review shows that the performance of the TS-vdW model is on par with that of other pairwise dispersion corrections. For example, for intermolecular interaction energies in the S66 data set, the TS-vdW correction added to PBE affords a mean absolute error of 0.4 kcal/mol and a maximum error of 1.5 kcal/mol, whereas the corresponding errors for PBE alone are 2.2 kcal/mol (mean) and 7.2 kcal/mol (maximum).

During the implementation of the TS-vdW scheme in Q-Chem, it was noted that evaluation of the free-atom volumes affords substantially different results as compared to the implementations in the FHI-aims and Quantum Espresso codes, e.g., $V_{\text{H,free}}$ = 8.68 a.u. (Q-Chem), 10.32 a.u. (FHI-aims), and 10.39 a.u. (Quantum Espresso) for hydrogen atom using the PBE functional. These discrepancies were traced to different implementations of Hirshfeld partitioning. In Q-Chem, the free-atom volumes are computed from an unrestricted atomic SCF calculation and then spherically averaged to obtain spherically-symmetric atomic densities. In FHI-aims and Quantum Espresso they are obtained by solving a one-dimensional radial Schrödinger equation, which automatically affords spherically-symmetric atomic densities but must be used with fractional occupation numbers for open-shell atoms. These differences could likely be ameliorated by reparameterizing the damping function in Eq. (5.45) for use with atomic volumes calculated self-consistently using Q-Chem, wherein the representation of the electronic structure is quite different as compared to that in either FHI-aims or Quantum Espresso. This has not been done, however, and the parameters were simply taken from a previous implementation. In order to reproduced TS-vdW dispersion energies obtained with FHI-aims or Quantum Espresso, it is possible to use this code in Q-Chem with scaling factors for the atomic Hirshfeld volumes, recommended values for which are obtained by linear regression, comparing Q-Chem atomic volumes to those obtained in FHI-aims. For full self-consistency, however, these scaling factors should not be used.

The TS-vdW dispersion energy is requested by setting TSVDW = TRUE. Energies and analytic gradients are available.

TSVDW
Flag to switch on the TS-vdW method
TYPE:
INTEGER
DEFAULT:
0
OPTIONS:
0 Do not apply TS-vdW. 1 Apply the TS-vdW method to obtain the TS-vdW energy. 2 Apply the TS-vdW method to obtain the TS-vdW energy and corresponding gradients.
RECOMMENDATION:
Since TS-vdW is itself a form of dispersion correction, it should not be used in conjunction with any of the dispersion corrections described in Section 5.7.2.

TSVDW_SR
Set custom value of the $s_{R}$ damping parameter
TYPE:
INTEGER
DEFAULT:
no default value defined
OPTIONS:
$n$ Corresponding to $n\cdot 10^{-4}$
RECOMMENDATION:
Use predefined values for supported functionals, otherwise consult Ref. 1092 and other relevant literature.

HIRSHFELD_CONV
Set different SCF convergence criterion for the calculation of the single-atom Hirshfeld calculations
TYPE:
INTEGER
DEFAULT:
same as SCF_CONVERGENCE
OPTIONS:
$n$ Corresponding to $10^{-n}$
RECOMMENDATION:
5

HIRSHMOD
Apply modifiers to the free-atom volumes used in the calculation of the scaled TS-vdW parameters
TYPE:
INTEGER
DEFAULT:
4
OPTIONS:
0 Do not apply modifiers to the Hirshfeld volumes. 1 Apply built-in modifier to H. 2 Apply built-in modifier to H and C. 3 Apply built-in modifier to H, C and N. 4 Apply built-in modifier to H, C, N and O
RECOMMENDATION:
Use the default

Example 5.13  Sample input illustrating a calculation of a water molecule, including the TS-vdW energy.

$molecule 0 1 O H 1 0.95 H 1 0.95 2 104.5$end

$rem BASIS 6-31G* METHOD PBE TSVDW TRUE !vdw settings HIRSHFELD_CONV 6 ! sets SCF_CONVERGENCE for single atom calculations HIRSHMOD 4 ! Apply modifiers to the free-atom volumes for H, C, N, and O$end


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