Valentin V. Karasiev, Samuel B. Trickey. Frank Discussion of the Status of Ground-State Orbital-Free DFT
Advances in Quantum Chemistry, vol. 71, pp. 221–245 (2015), 2015-06-17
Abstract: F.E. Harris has been a significant partner in our work on orbital-free density functional
approximations for use in ab initio molecular dynamics. Here we mention briefly the
essential progress in single-point functionals since our original paper (2006). Then
we focus on the advantages and limitations of generalized gradient approximation
(GGA) noninteracting kinetic energy (KE) functionals. We reconsider the constraints provided
by near-origin conditions in atomic-like systems and their relationship to regularized
versus physical external potentials. Then we seek the best empirical GGA for the
noninteracting KE for a modest-sized set of molecules with well-defined near-origin
behavior of their densities. The search is motivated by a desire for insight into GGA limitations
and for a target for constraint-based development.