Density Functional for Anisotropic Fluids

We propose a density functional for anisotropic fluids of hard body particles. It interpolates between the well-established geometrically based Rosenfeld functional for hard spheres and the Onsager functional for elongated rods. We test the new approach by calculating the location of the the nematic-isotropic transition in systems of hard spherocylinders and hard ellipsoids. The results are compared with existing simulation data. Our functional predicts the location of the transition much more accurately than the Onsager functional, and almost as good as the theory by Parsons and Lee. We argue that it might be suited to study inhomogeneous systems.Comment: To appear in J. Physics: Condensed Matte

Theory of asymmetric non-additive binary hard-sphere mixtures

We show 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 non-additive 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 we determine the zero, one, and two-body contribution to the effective Hamiltonian. We demonstrate that even small degrees of positive or negative non-additivity have significant effect on the shape of the depletion potential. The second virial coefficient $B_2$, corresponding to the effective pair interaction between two big spheres, is found to be a sensitive measure of the effects of non-additivity. The variation of $B_2$ with the density of the small spheres shows significantly different behavior for additive, slightly positive and slightly negative non-additive mixtures. We discuss the possible repercussions of these results for the phase behavior of binary hard-sphere mixtures and suggest that measurements of $B_2$ might provide a means of determining the degree of non-additivity in real colloidal mixtures

Density-functional, Landau, and Onsager theories of the isotropic-nematic transition of hard ellipsoids

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