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Isotropic-nematic phase transition of uniaxial variable softness prolate and oblate ellipsoids.
Journal of Chemical Physics 2017 April 29
Onsager's theory of the isotropic-nematic phase separation of rod shaped particles is generalized to include particle softness and attractions in the anisotropic interparticle force field. The procedure separates a scaled radial component from the angular integral part, the latter being treated in essentially the same way as in the original Onsager formulation. Building on previous treatments of more idealised hard-core particle models, this is a step toward representing more realistic rod-like systems and also allowing temperature (and in principle specific chemical factors) to be included at a coarse grained level in the theory. The focus of the study is on the coexisting concentrations and associated coexistence properties. Prolate and oblate ellipsoids are considered in both the small and very large aspect ratio limits. Approximations to the terms in the angular integrals derived assuming the very large (prolate) and very small (oblate) aspect ratios limits are compared with the formally exact treatment. The approximation for the second virial coefficient matches the exact solution for aspect ratios above about 20 for the prolate ellipsoids and less than ca. 0.05 for the oblate ellipsoids from the numerical evaluation of the angular integrals. The temperature dependence of the coexistence density could be used to help determine the interaction potential of two molecules. The method works at temperatures above a certain threshold temperature where the second virial coefficient is positive.
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