Entropy and Fluid-Fluid Separation in Nonadditive Hard-Sphere Mixtures

We study the equilibrium behavior of a two-component mixture of equal-sized, nonadditive hard spheres with an interspecies collision diameter that is larger than that of each component. We calculate the thermodynamic and structural properties by simulating a system of 4000 particles in a canonical ensemble through a standard Monte Carlo technique. The phase behavior of the model is analyzed through a multiparticle correlation expansion of the statistical entropy whose prediction on the existence of a fluid-fluid separation threshold compares favorably with independent results on the phase coexistence line