Confirmation of the PPLB Derivative Discontinuity: Exact Chemical Potential at Finite Temperatures of a Model System.

Abstract

The landmark 1982 work of Perdew, Parr, Levy, and Balduz (often called PPLB) laid the foundation for our modern understanding of the role of the derivative discontinuity in density functional theory, which drives much development to account for its effects. A simple model for the chemical potential at vanishing temperature played a crucial role in their argument. We investigate the validity of this model in the simplest nontrivial system to which it can be applied and which can be easily solved exactly, the Hubbard dimer. We find exact agreement in the crucial zero-temperature limit and show the model remains accurate for a significant range of temperatures. We identify how this range depends on the strength of correlations. We extend the model to approximate free energies accounting for the derivative discontinuity, a feature missing in standard semilocal approximations. We provide a correction to this approximation to yield even more accurate free energies. We discuss the relevance of these results for warm dense matter.