Exchange-correlation potential with correct asymptotic behavior

Abstract

In this work we analyze the properties of the exchange-correlation potential in the Kohn-Sham form of density-functional theory, which leads to requirements for approximate potentials. Fulfilment of these requirements is checked for existing gradient-corrected potentials. In order to examine the behavior of approximate potentials over all space we compare these potentials with exact Kohn-Sham potentials calculated from correlated densities using a newly developed iterative procedure. The main failures in the existing gradient-corrected potentials arise in the asymptotic region of the atom where these potentials decay too fast and at the atomic nucleus where the potentials exhibit a Coulomb-like singular behavior. We show that the main errors can be corrected by a simple potential in terms of the density and its gradients leading to considerably improved one-electron energies compared to the local-density approximation. For Be and Ne it is shown that the electron density is improved in the outer region.