Fragment-based treatment of delocalization and static correlation errors in density-functional theory.

Abstract

One of the most important open challenges in modern Kohn-Sham (KS) density-functional theory (DFT) is the correct treatment of systems involving fractional electron charges and spins. Approximate exchange-correlation functionals struggle with such systems, leading to pervasive delocalization and static correlation errors. We demonstrate how these errors, which plague density-functional calculations of bond-stretching processes, can be avoided by employing the alternative framework of partition density-functional theory (PDFT) even using the local density approximation for the fragments. Our method is illustrated with explicit calculations on simple systems exhibiting delocalization and static-correlation errors, stretched H2 (+), H2, He2 (+), Li2 (+), and Li2. In all these cases, our method leads to greatly improved dissociation-energy curves. The effective KS potential corresponding to our self-consistent solutions displays key features around the bond midpoint; these are known to be present in the exact KS potential, but are absent from most approximate KS potentials and are essential for the correct description of electron dynamics.