Incorporating molecular scale structure into the van der Waals theory of the liquid-vapor interface

TL;DR

This paper introduces a new theoretical framework that integrates molecular scale details into the classical van der Waals model to better predict liquid-vapor interface properties, aligning well with simulation data.

Contribution

A novel, general theory of nonuniform fluids that incorporates molecular scale information into the van der Waals framework for interfaces.

Findings

Accurately predicts interface profiles across temperatures.

Provides surface tension estimates matching simulation results.

Clarifies why capillary wave effects are absent in the model.

Abstract

We have developed a new and general theory of nonuniform fluids that naturally incorporates molecular scale information into the classical van der Waals theory of slowly varying interfaces. Here the theory is applied to the liquid-vapor interface of a Lennard-Jones fluid. The method combines a molecular field treatment of the effects of unbalanced attractive forces with a locally optimal use of linear response theory to approximate fluid structure by that of the associated (hard sphere like) reference fluid. Our approach avoids many of the conceptual problems that arise in the classical theory and shows why capillary wave effects are not included in the theory. The general theory and a simplified version gives results for the interface profile and surface tension for states with different temperatures and potential energy cutoffs that compare very favorably with simulation data.