Chapter 8 - The Gibbs Ensemble

Abstract

The Gibbs ensemble method has become the technique par excellence to study vapor-liquid and liquid-liquid equilibria. However, like simulations in the grand-canonical ensemble, the method relies on a reasonable number of successful particle insertions to achieve compositional equilibrium. As a consequence, the Gibbs ensemble method is not very efficient for studying equilibria involving very dense phases. However, there is a technique that greatly facilitates the numerical study of phase equilibria of dense phases. The success of the Gibbs ensemble method relies on the possibility of exchanging particles between the two coexisting phases. The Gibbs ensemble technique is used to study the phase behavior of a variety of systems. This chapter discusses some applications of this method in dense liquids and polar and ionic fluids.