Inadequacy of the Lorentz-Berthelot combining rules for accurate predictions of equilibrium properties by molecular simulation

Abstract

Though molecular beam experiments have revealed deficiencies in the Lorentz-Berthelot combining rules, these rules are still used widely to parametrize effective pair potential models or to calculate the thermodynamic properties of mixtures. Gibbs ensemble Monte Carlo and isothermal isobaric Monte Carlo simulations were used to compute the liquid-vapour phase equilibria and the liquid properties of binary mixtures of rare gases modelled by effective pair potentials. Three sets of simple combining rules were tested in this work: the commonly used Lorentz-Berthelot rules, the Kong rules (Kong, J., 1973, J. chem. Phys., 59, 2464) and the Waldman-Hagler rules (Waldman, M., and Hagler, A. T., 1993, J. comput. Chem., 14, 1077). These three sets of rules do not require any additional parameter. It is shown that: (1) the choice of a set of combining rules has a significant effect on the thermodynamic properties, (2) using the Lorentz-Berthelot rules yields significant deviations from experiment and (3) the Kong rules provide a much better description of the mixture properties both for coexistence curves and liquid properties. We therefore recommend the use of the Kong rules instead of the Lorentz-Berthelot when parametrizing potential models.