Assessing the accuracy of the van der Waals density functionals for rare-gas and small molecular systems

Abstract

The precise description of chemical bonds with different natures is a prerequisite for an accurate electronic structure method. The van der Waals density functional is a promising approach that meets such a requirement. Nevertheless, the accuracy should be assessed for a variety of materials to test the robustness of the method. We present benchmark calculations for weakly interacting molecular complexes and rare-gas systems as well as covalently bound molecular systems, in order to assess the accuracy and applicability of rev-vdW-DF2, a recently proposed variant [I. Hamada, Phys. Rev. B 89, 121103 (2014)] of the van der Waals density functional. It is shown that although the calculated atomization energies for small molecules are less accurate rev-vdW-DF2 describes the interaction energy curves for the weakly interacting molecules and rare-gas complexes, as well as the bond lengths of diatomic molecules, reasonably well.