Accurate and simple density functional for the electronic exchange energy: Generalized gradient approximation

Abstract

The electronic exchange energy as a functional of the density may be approximated as Ex[n]=Ax d3rn43F(s), where s=n|2kFn, kF=(32n)13, and F(s)=(1+1.296s2+14s4+0.2s6)115. The basis for this approximation is the gradient expansion of the exchange hole, with real-space cutoffs chosen to guarantee that the hole is negative everywhere and represents a deficit of one electron. Unlike the previously publsihed version of it, this functional is simple enough to be applied routinely in self-consistent calculations for atoms, molecules, and solids. Calculated exchange energies for atoms fall within 1% of Hartree-Fock values. Significant improvements over other simple functionals are also found in the exchange contributions to the valence-shell removal energy of an atom and to the surface energy of jellium within the infinite barrier model. © 1986 The American Physical Society.