Equilibria between solid, liquid, and vapor phases in binary Lennard–Jones mixtures

Abstract

We have used Monte Carlo simulation and the Gibbs–Duhem integration technique to calculate temperature–composition and pressure–temperature phase diagrams for binary Lennard–Jones mixtures. We systematically explore Lennard–Jones parameter space to demonstrate how the features of these phase diagrams change as a function of diameter ratio, well-depth ratio, binary interaction parameter, and pressure. We find a number of cases in which the vapor–liquid and liquid–liquid equilibria become metastable with respect to the solid–liquid and solid–vapor equilibria.