Monte Carlo methods for phase equilibria of fluids

Publisher Website
Google Scholar
Abstract
This article presents an overview of Monte Carlo methods for simulations of the phase behaviour of fluids. The Gibbs ensemble method and histogram-reweighting Monte Carlo techniques are described in detail. The Gibbs ensemble method is based on simulations of two regions coupled via volume change and particle transfer moves so that the conditions for phase coexistence are satisfied in a statistical sense. Histogram-reweighting methods obtain the free energy of a system over a broad range of conditions from a small set of grand canonical Monte Carlo calculations. The histogram methods can produce highly accurate data, especially in the vicinity of critical points. Other methods described briefly include interfacial simulations, the NPT + test particle method, Gibbs-Duhem integration and pseudo-ensembles. Configurational-bias sampling techniques and expanded ensembles can be used for multisegment molecules to increase the efficiency of the simulations. The last section of the review covers applications to both model and realistic systems that have appeared since 1995.