Role of the core-valence interaction for pseudopotential calculations with exact exchange

Abstract

Standard normconserving pseudopotentials for the exact exchange energy functional of density functional theory exhibit a spurious long-range structure induced by the core-valence interaction. In this contribution the origin of this structure and its implications for the description of atoms, molecules, and solids is analyzed in detail. It is found that bond distances and energies obtained can be seriously in error, in particular for solids. Based on this analysis a parameter-free, self-consistent scheme for the elimination of the spurious feature is suggested. The resulting pseudopotentials predict binding properties of molecules and solids which, on average, are more accurate than those obtained with the corresponding local density approximation pseudopotentials.