A revisit of the density gradient theory and the mean field theory for the vapor-liquid interface system

TL;DR

This paper revisits the density gradient and mean-field theories for vapor-liquid interfaces, proposing a new mean-field crossover based on Maxwell construction that improves predictions of interfacial properties and clarifies phase behavior.

Contribution

It introduces a physically consistent mean-field crossover as the dividing interface, extending the Widom line concept and providing a comprehensive analysis of vapor-liquid phase space.

Findings

The mean-field dividing interface extends the Widom line into the coexistence region.

The intrinsic heat capacity exhibits unconventional behavior, being positive at low temperatures and negative at high temperatures.

A complete mean-field equation of state with three solutions for vapor-liquid equilibrium is presented.

Abstract

In this work we define a mean-field crossover generated by the Maxwell construction as the dividing interface for the vapor-liquid interface area. A highly accurate density-profile equation is thus derived, which is physically favorable and leads to reliable predictions of interfacial properties. By using the density gradient theory and a mean-field equation of sate for the Lennard-Jones fluid, we are able to extensively explore the interface system in terms of the Gibbs free energy, the Helmholtz free energy and heat capacity. The results show that the mean-field dividing interface is the natural extension of the Widom line into the coexistence region. Hence the entire phase space is coherently divided into liquid-like and gas-like regions in all three (temperature-pressure-volume) planes. Some unconventional behaviors are observed for the intrinsic heat capacity, being positive in low temperature region while negative in high temperature region. Finally, a complete picture of the mean-field equation of state is unfolded: all three solutions to a vapor-liquid equilibrium problem have their respective significances.