Derivative discontinuities in density functional theory

Abstract

Fifty years after the original formulation of density functional theory (DFT), subtle consequences of the mathematical mappings underlying its formalism continue to merit new views. In this article, we discuss the origin, the importance, and the challenges associated with finding the derivative discontinuity of the exchange-correlation (XC) energy of DFT at integer–electron numbers. We show how even the energy of a quantum electron gas with finite volume and number of electrons displays such derivative discontinuities, but continuous density functional approximations to the XC functional miss them entirely. We discuss some of the practical problems that arise due to this lack of derivative discontinuities in standard functionals, and explain new ways to recover them.