Accurate interaction energies at DFT level by means of an efficient dispersion correction

TL;DR

This paper introduces an efficient dispersion correction method for DFT calculations that improves accuracy of interaction energies, especially for low-symmetry complexes, validated against high-level CCSD(T) results.

Contribution

The method combines dispersion energy correction with atomic polarizability partitioning, including anisotropic effects, to enhance DFT accuracy without damping functions.

Findings

Achieves high accuracy in interaction energies for various functionals.

TPSS functional performs best among tested functionals.

Method closely matches CCSD(T) benchmark energies.

Abstract

This paper presents an approach for obtaining accurate interaction energies at the DFT level for systems where dispersion interactions are important. This approach combines Becke and Johnson's [J. Chem. Phys. 127, 154108 (2007)] method for the evaluation of dispersion energy corrections and a Hirshfeld method for partitioning of molecular polarizability tensors into atomic contributions. Due to the availability of atomic polarizability tensors, the method is extended to incorporate anisotropic contributions, which prove to be important for complexes of lower symmetry. The method is validated for a set of eighteen complexes, for which interaction energies were obtained with the B3LYP, PBE and TPSS functionals combined with the aug-cc-pVTZ basis set and compared with the values obtained at CCSD(T) level extrapolated to a complete basis set limit. It is shown that very good quality interaction energies can be obtained by the proposed method for each of the examined functionals, the overall performance of the TPSS functional being the best, which with a slope of 1.00 in the linear regression equation and a constant term of only 0.1 kcal/mol allows to obtain accurate interaction energies without any need of a damping function for complexes close to their exact equilibrium geometry.