Integral equations for simple fluids in a general reference functional approach

TL;DR

This paper develops a general functional approach to derive integral equations for inhomogeneous fluid mixtures, enabling accurate predictions of their thermodynamic properties and behaviors near interfaces, exemplified by a Lennard-Jones fluid near a hard wall.

Contribution

It introduces a reference functional method for integral equations of inhomogeneous fluids, improving the analysis of correlation functions and thermodynamics beyond second order.

Findings

Accurate equation of state for Lennard-Jones fluid

Good agreement with Maxwell construction for coexisting densities

Effective description of wall-fluid interactions and drying phenomena

Abstract

The integral equations for the correlation functions of an inhomogeneous fluid mixture are derived using a functional Taylor expansion of the free energy around an inhomogeneous equilibrium distribution. The system of equations is closed by the introduction of a reference functional for the correlations beyond second order in the density difference from the equilibrium distribution. Explicit expressions are obtained for energies required to insert particles of the fluid mixture into the inhomogeneous system. The approach is illustrated by the determination of the equation of state of a simple, truncated Lennard--Jones fluid and the analysis of the behavior of this fluid near a hard wall. The wall--fluid integral equation exhibits complete drying and the corresponding coexisting densities are in good agreement with those obtained from the standard (Maxwell) construction applied to the bulk fluid. Self--consistency of the approach is examined by analyzing the virial/compressibility routes to the equation of state and the Gibbs--Duhem relation for the bulk fluid, and the contact density sum rule and the Gibbs adsorption equation for the hard wall problem. For the bulk fluid, we find good self--consistency for stable states outside the critical region. For the hard wall problem, the Gibbs adsorption equation is fulfilled very well near phase coexistence where the adsorption is large.For the contact density sum rule, we find some deviationsnear coexistence due to a slight disagreement between the coexisting density for the gas phase obtained from the Maxwell construction and from complete drying at the hard wall.