Laplacian-level density functionals for the kinetic energy density and exchange-correlation energy

Abstract

We construct a Laplacian-level meta-generalized gradient approximation (meta-GGA) for the non-interacting (Kohn-Sham orbital) positive kinetic energy density $τ$ of an electronic ground state of density $n$. This meta-GGA is designed to recover the fourth-order gradient expansion $τ^{GE4}$ in the appropiate slowly-varying limit and the von Weizsäcker expression $τ^{W}=|\nabla n|^2/(8n)$ in the rapidly-varying limit. It is constrained to satisfy the rigorous lower bound $τ^{W}(\mathbf{r})\leqτ(\mathbf{r})$. Our meta-GGA is typically a strong improvement over the gradient expansion of $τ$ for atoms, spherical jellium clusters, jellium surfaces, the Airy gas, Hooke's atom, one-electron Gaussian density, quasi-two dimensional electron gas, and nonuniformly-scaled hydrogen atom. We also construct a Laplacian-level meta-GGA for exchange and correlation by employing our approximate $τ$ in the Tao, Perdew, Staroverov and Scuseria (TPSS) meta-GGA density functional. The Laplacian-level TPSS gives almost the same exchange-correlation enhancement factors and energies as the full TPSS, suggesting that $τ$ and $\nabla^2 n$ carry about the same information beyond that carried by $n$ and $\nabla n$. Our kinetic energy density integrates to an orbital-free kinetic energy functional that is about as accurate as the fourth-order gradient expansion for many real densities (with noticeable improvement in molecular atomization energies), but considerably more accurate for rapidly-varying ones.