Van der Waals Interactions in Density-Functional Theory: Rare-Gas Diatomics.

Abstract

The application of conventional GGA and meta-GGA density functionals to van der Waals interactions is fraught with difficulties. Conventional functionals do not contain the physics of the dispersion interaction. To make matters worse, the exchange part alone can yield anything from severe overbinding to severe over-repulsion depending on the choice of functional. We have assessed a variety of exchange GGAs for their ability to reproduce exact Hartree-Fock repulsion energies in rare-gas systems, and we find that PW86 [ Phys. Rev. B 1986 , 33 , 8800 ] performs remarkably well. The addition of a dynamical correlation GGA and the nonempirical dispersion model of Becke and Johnson [ J. Chem. Phys. 2007 , 127 , 154108 ] to PW86 gives a simple GGA plus dispersion theory yielding excellent rare-gas interaction curves for pairs involving He through Kr, with only two adjustable parameters for damping of the dispersion terms.