Pair correlation functions and phase separation in a two component point Yukawa fluid

Abstract

We investigate the structure of a binary mixture of particles interacting via purely repulsive (point) Yukawa pair potentials with a common inverse screening length $\lambda$. Using the hyper-netted chain closure to the Ornstein-Zernike equations, we find that for a system with `ideal' (Berthelot mixing rule) pair potential parameters for the interaction between unlike species, the asymptotic decay of the total correlation functions crosses over from monotonic to damped oscillatory on increasing the fluid total density at fixed composition. This gives rise to a Kirkwood line in the phase diagram. We also consider a `non-ideal' system, in which the Berthelot mixing rule is multiplied by a factor $(1+\delta )$. For any $\delta >0$ the system exhibits fluid-fluid phase separation and remarkably the ultimate decay of the correlation functions is now monotonic for all (mixture) state points. Only in the limit of vanishing concentration of either species does one find oscillatory decay extending to $r=\infty$. In the non-ideal case the simple random phase approximation provides a good description of the phase separation and the accompanying Lifshitz line.

11 pages, 6 figures. Accepted for publication in J. Chem. Phys

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