External fields, density functionals, and the Gibbs inequality

Abstract

By combining the upper and lower bounds to the free energy as given by the Gibbs inequality for two systems with the same intermolecular interactions but with external fields differing from each other only in a finite region of space Gamma, we show that the corresponding equilibrium densities must also differ from each other somewhere in Gamma. We note that the basic equations of density functional theory arise naturally from a simple rearrangement and reinterpretation of the terms in the upper bound Gibbs inequality for such systems and briefly discuss some of the complications that occur when the intermolecular interactions of the two systems also differ.