Role of the core-valence interaction for pseudopotential calculations withexact exchange - art. no. 125111

Standard normconserving pseudopotentials for the exact exchange energy func tional of density functional theory exhibit a spurious long-range structure induced by the core-valence interaction. In this contribution the origin o f this structure and its implications for the description of atoms, molecul es, and solids is analyzed in detail. It is found that bond distances and e nergies obtained can be seriously in error, in particular for solids. Based on this analysis a parameter-free, self-consistent scheme for the eliminat ion of the spurious feature is suggested. The resulting pseudopotentials pr edict binding properties of molecules and solids which, on average, are mor e accurate than those obtained with the corresponding local density approxi mation pseudopotentials.