NpT-ensemble Monte Carlo calculations for binary liquid mixtures

Abstract

A Monte Carlo method for the calculation of thermodynamic properties in the isothermal-isobaric ensemble is described. Application is made to the calculation of excess thermodynamic properties (enthalpy, volume and Gibbs free energy) of binary mixtures of Lennard-Jones 12–6 liquids. Comparison is made with the predictions of a number of theories of liquid mixtures; the so-called van der Waals one-fluid model and the variational theory of Mansoori and Leland are both found to give excellent results. The accuracy attainable in estimates of the excess properties is discussed in terms of statistical fluctuations in various calculated quantities and the advantages and disadvantages of the method are examined in relation to calculations by the more familiar constant-volume method.