Structure of classical liquid of charged hard spheres and point ions

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Abstract
Because of current interest in charged fluids the problem of the structure of a mixture of charged hard spheres of unequal diameters sigma 1 and sigma 2 is studied in the limit sigma 1/ sigma 2 to 0. In particular, the mean spherical model (MSM) has been solved in this limit. The thermodynamics of the mixture is discussed and some typical results for the partial radial distributions are presented. The MSM has the defect in the limiting case sigma 1/ sigma 2 to 0 that the pair correlation function of the point ions always becomes negative at sufficiently short distances. Therefore, to test the predictions of the model, Monte Carlo calculations are presented for this same system for two molten-like states. One of these is just above the expected melting point and the other at an extremely high temperature. In the light of these results, the model's relevance to real systems is briefly discussed, CuCl BeF2 and HF each being referred to. An interesting property of the model which we demonstrate is that polymerization can occur.