Semiempirical van der Waals correction to the density functional description of solids and molecular structures

TLDR

The correction depends solely on the properties of the two atoms, independent of their environment, and is numerically very efficient. The study investigates the influence of a simple semiempirical van der Waals correction on dispersive, covalent, and ionic bonds in density functional theory and probes its universality across a range of solids and molecular systems with covalent, heteropolar, and vdW bonds. The correction is based on the asymptotic London form of dispersive forces with a damping function for each atom pair, and is tested against generalized gradient approximation, local density approximation, and reference experimental or quantum chemistry values.

Abstract

The influence of a simple semiempirical van der Waals (vdW) correction on the description of dispersive, covalent, and ionic bonds within density functional theory is studied. The correction is based on the asymptotic London form of dispersive forces and a damping function for each pair of atoms. It thus depends solely on the properties of the two atoms irrespective of their environment and is numerically very efficient. The correction is tested in comparison with results obtained using the generalized gradient approximation or the local density approximation for exchange and correlation. The results are also compared with reference values from experiment or quantum chemistry methods. In order to probe the universality and transferability of the semiempirical vdW correction, a range of solids and molecular systems with covalent, heteropolar, and vdW bonds are studied.