Excess properties of liquid mixtures from computer simulation: a coupling-parameter approach to the determination of their dependence on molecular asymmetry

Abstract

A computer simulation technique is developed for the accurate determination of the change in the excess properties of binary model mixtures due to deviations of the unlike interaction parameters from the Lorentz-Berthelot (LB) combining rules. The technique avoids the explicit calculation of excess (mixing) properties, and the subsequent subtraction. The method requires a single isobaric-isothermal simulation of the reference Lorentz-Berthelot mixture, regardless of the extent of the deviations. The extension of the present approach to the general case of non-Lorentz-Berthelot reference systems is also discussed.