Fluids of hard natural and Gaussian ellipsoids: A comparative study by integral equation theories

Abstract

The hard Gaussian overlap (HGO) model for ellipsoids is compared to the hard ellipsoid of revolution (HER) model, in the isotropic fluid phase and within the framework of the Percus-Yevick (PY) and hypernetted chain (HNC) integral equation theories. The former model is often used in place of the latter in many approximate theories. Since the HGO model slightly overestimates the contact distance when the two ellipsoids are perpendicular to each other, it leads to small differences in the Mayer function of the two models, but nearly none in the integrals of these functions and particularly for the second virial coefficients. However, it leads to notable differences in the pair correlation functions, as obtained by the Percus-Yevick and the hypernetted chain theories, especially at high densities. The prediction of the stability of the isotropic phase with respect to orientational order, at high densities, is notably influenced by these small differences. Both theories predict that, for same aspect ratios, the HGO model overestimates the ordering, when compared to the HER model. This explains why the PY approximation predicts ordering for the HGO model with aspect ratio of 1:3, while it does not for the HER model, in accordance with the very first integral equation results obtained for this system, and at variance with many opposite claims from subsequent publications that used the HGO model in place of the HER model.