This paper presents an approach for obtaining accurate interaction energies at the density functional theory 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 18 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 the 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.
Accurate interaction energies at density functional theory level by means of an efficient dispersion correction
Alisa Krishtal, Kenno Vanommeslaeghe, András Olasz, Tamás Veszprémi, Christian Van Alsenoy, Paul Geerlings; Accurate interaction energies at density functional theory level by means of an efficient dispersion correction. J. Chem. Phys. 7 May 2009; 130 (17): 174101. https://doi.org/10.1063/1.3126248
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