"Kohn-Shamification" of the classical density-functional theory of inhomogeneous polar molecular liquids with application to liquid hydrogen chloride

TL;DR

This paper introduces a Kohn-Sham-inspired approach to classical density-functional theory for inhomogeneous polar molecular liquids, providing a more accurate and computationally feasible method exemplified by liquid hydrogen chloride.

Contribution

It adapts Kohn-Sham methodology to classical molecular liquids, enabling accurate free-energy functional calculations using effective potentials.

Findings

Accurate free-energy functional formulation for polar liquids.

Effective potentials simplify complex molecular interactions.

Application to liquid HCl demonstrates method's effectiveness.

Abstract

The Gordian knot of density-functional theories for classical molecular liquids remains finding an accurate free-energy functional in terms of the densities of the atomic sites of the molecules. Following Kohn and Sham, we show how to solve this problem by considering noninteracting molecules in a set of effective potentials. This shift in perspective leads to an accurate and computationally tractable description in terms of simple three-dimensional functions. We also treat both the linear- and saturation- dielectric responses of polar systems, presenting liquid hydrogen chloride as a case study.