Theory of asymmetric nonadditive binary hard-sphere mixtures.

It is shown that the formal procedure of integrating out the degrees of freedom of the small spheres in a binary hard-sphere mixture works equally well for nonadditive as it does for additive mixtures. For highly asymmetric mixtures (small size ratios) the resulting effective Hamiltonian of the one-component fluid of big spheres, which consists of an infinite number of many-body interactions, should be accurately approximated by truncating after the term describing the effective pair interaction. Using a density functional treatment developed originally for additive hard-sphere mixtures the zero, one, and two-body contribution to the effective Hamiltonian are determined. It is demonstrated that even small degrees of positive or negative nonadditivity have significant effect on the shape of the depletion potential. The second virial coefficient B2, corresponding to the effective pair interaction between two big spheres, is found to be a sensitive measure of the effects of nonadditivity. The variation of B2 with the density of the small spheres shows significantly different behavior for additive, slightly positive and slightly negative nonadditive mixtures. Possible repercussions of these results for the phase behavior of binary hard-sphere mixtures are discussed and it is suggested that measurements of B2 might provide a means of determining the degree of nonadditivity in real colloidal mixtures.