Entropy density functional universality: Correlation, response, and entropic Ornstein-Zernike structure

Abstract

We give a comprehensive account of the recent entropy density functional theory for the equilibrium statistical mechanics of classical many-body systems (arXiv:2606.28240). The approach is formally exact and based on a joint grand potential minimization principle for the one-body density and the global pair distance distribution. These variational fields depend respectively on position and on scalar distance, which retains the low computational complexity of standard density functional theory. Correlations effects are contained in a unique excess entropy functional, which is universal across all systems with pairwise interparticle potentials. Functional differentiation yields entropic direct correlation functionals that generate entropic response and fluctuation correlation functions via coupled Ornstein-Zernike equations. Two alternative proofs are given for the existence and uniqueness of the underlying metadensity functional map, based on generalizations of either Levy's constrained search method or Mermin-Evans proof by contradiction. Simple excess entropy approximations yield the standard mean-field and second-virial excess free energy density functionals. We describe exact entropic functional line integrals, make connections to the recent one-body fluctuation profiles, and generalize the entropy approach beyond pairwise interparticle potentials.