Effect of orbital-overlap dependence in density functionals

Abstract

The semilocal meta generalized gradient approximation (MGGA) for the exchange-correlation functional of Kohn-Sham (KS) density functional theory can yield accurate ground-state energies simultaneously for atoms, molecules, surfaces, and solids, due to the inclusion of kinetic energy density as an input. We study for the first time the effect and importance of the dependence of MGGA on the kinetic energy density through the dimensionless inhomogeneity parameter, $\alpha$, that characterizes the extent of orbital overlap. This leads to a simple and wholly new MGGA exchange functional, which interpolates between the single-orbital regime, where $\alpha=0$, and the slowly varying density regime, where $\alpha \approx 1$, and then extrapolates to $\alpha \to \infty$. When combined with a variant of the Perdew-Burke-Erzerhof (PBE) GGA correlation, the resulting MGGA performs equally well for atoms, molecules, surfaces, and solids.