Laplacian-based generalized gradient approximations for the exchange energy

Abstract

It is well known that in the gradient expansion approximation to density functional theory (DFT) the gradient and Laplacian of the density make interchangeable contributions to the exchange correlation (XC) energy. This is an arbitrary "gauge" freedom for building DFT models, normally used to eliminate the Laplacian from the generalized gradient approximation (GGA) level of DFT development. We explore the implications of keeping the Laplacian at this level of DFT, to develop a model that fits the known behavior of the XC hole, which can only be described as a system average in conventional GGA. We generate a family of exchange models that obey the same constraints as conventional GGA's, but which in addition have a finite-valued potential at the atomic nucleus unlike GGA's. These are tested against exact densities and exchange potentials for small atoms, and for constraints chosen to reproduce the SOGGA and the APBE variants of the GGA. The model reliably reproduces exchange energies of closed shell atoms, once constraints such the local Lieb-Oxford bound, whose effects depend upon choice of energy-density gauge, are recast in invariant form.

Visualisation and orbital-free parametrisation of the large-Z scaling of the kinetic energy density of atoms

“…Adapting a form recently used to construct a ∇ 2 n-based exchange function [66] results in the enhancement factor…”