Theoretical and computer simulation study of phase coexistence of nonadditive hard-disk mixtures

We have studied the equation of state (EOS) and the equilibrium behavior of a two-component mixture of equal-sized, nonadditive hard disks with an interspecies collision diameter that is larger than that of each component. For this purpose, we have calculated the fifth virial coefficient by evaluating numerically the irreducible cluster integrals by a Monte Carlo method. This information is used to calculate both the virial equation of state and an equation of state based on a resummation of the virial expansion. Then, the fluid-fluid phase coexistence boundaries are determined by integrating the EOS so as to obtain the free energy of the system. Canonical and Gibbs ensemble Monte Carlo simulations over a wide range of nonadditivity are also performed in order to provide a benchmark to the theoretical predictions.