Self-consistent implementation of nonlocal exchange and correlation in a Gaussian density-functional method.

Abstract

The gradient-expansion approximation (GEA) and the generalized gradient approximation (GGA) to nonlocal exchange energy in concert with the nonlocal correlation energy functional of Perdew [Phys. Rev. B 33, 8822 (1986)] are analyzed when implemented in a fully self-consistent way in conjunction with the Vosko-Wilk-Nusair parametrization for the local exchange-correlation energy. It is shown that the lowest-order gradient expansion, even with corrected asymptotic behavior in the large-density-gradient limit, is still unsatisfactory in the chemically important region of electron densities where the basic assumption of the GEA (\ensuremath{\Vert}\ensuremath{\nabla}n\ensuremath{\Vert}/2${\mathit{k}}_{\mathit{F}}$n1) breaks down. In contrast, the GGA expansion behaves better. A shift by a constant additive term of an effective one-body Kohn-Sham potential in concert with the GGA nonlocal functional provides, within the framework of density-functional theory, a way of interpreting excitation energies. The nonlocal functionals significantly improve binding energies. The resulting nonlocal exchange-correlation potential is state independent; thus the present method is convenient from the computational point of view. Applications are presented for a number of atoms and small molecules, including ${\mathrm{O}}_{2}$, ${\mathrm{Mg}}_{2}$, ${\mathrm{CH}}_{2}$, and for a transition-metal cluster, ${\mathrm{Ni}}_{4}$.