Solid–liquid phase coexistence of the Lennard-Jones system through phase-switch Monte Carlo simulation

The phase-switch Monte Carlo method of Wilding and Bruce [Phys. Rev. Lett. 85, 5138 (2000)] is extended to enable calculation of solid-liquid phase coexistence for soft potentials. The method directly accesses coexistence information about a system while avoiding simulation of the interfacial region. Order parameters are introduced that allow one to define a path that connects liquid and crystalline phases. Transition matrix methods are employed to bias the sampling such that both phases are sampled in a rapid and efficient manner. Coexistence properties are determined through an analysis of specific volume probability distributions, which are generated naturally during a biased simulation. The approach is demonstrated with the Lennard-Jones system. Finite-size effects are examined and compared to those for the hard sphere system. In addition, two techniques are considered for accounting for long-range interactions. The methodology presented here is general and therefore provides a basis for its application to other soft systems.