On the equivalence of self-consistent equations for nonuniform liquids: a unified description of the various modifications

TL;DR

This paper unifies various self-consistent equations used for modeling non-uniform liquids under external fields, demonstrating their equivalence through a hybrid theoretical framework combining density functional theory and statistical field theory.

Contribution

It introduces a unified equation that explains the diversity of previous self-consistent equations for non-uniform liquids, establishing their fundamental equivalence.

Findings

Derived a novel grand-potential density functional.

Proved the equivalence of multiple SC equations.

Provided a unified theoretical framework for non-uniform liquids.

Abstract

A variety of self-consistent (SC) equations have been proposed for non-uniform states of liquid particles under external fields, including adsorbed states at solid substrates and confined states in pores. External fields represent not only confining geometries but also fixed solutes. We consider SC equations ranging from the modified Poisson-Boltzmann equations for the Coulomb potential to the hydrostatic linear response equation for the equilibrium density distribution of Lennard-Jones fluids. Here, we present a unified equation that explains the apparent diversity of previous forms and proves the equivalence of various SC equations. This unified description of SC equations is obtained from a hybrid method combining the conventional density functional theory and statistical field theory. The Gaussian approximation of density fluctuations around a mean-field distribution is performed based on the developed hybrid framework, allowing us to derive a novel form of the grand-potential density functional that provides the unified SC equation for equilibrium density.