Structure and freezing of a fluid of long elongated molecules

Abstract

The pair correlation functions of a fluid of long elongated molecules interacting via the Gay-Berne pair potential are calculated using the Percus-Yevick integral equation theory. Numerical accuracy has been examined by considering a large number of spherical harmonic coefficients for each orientation-dependent functions for a system of molecules having a length-to-breadth ratio equal to 4.4 at different densities and temperatures. The pair correlation functions of the isotropic fluid found from the Percus-Yevick theory have been used in the density-functional theory to locate the isotropic-nematic, isotropic-smectic A and nematic-smectic A transitions. It is found that at low temperatures the fluid freezes directly into the smectic A phase on increasing the density. The nematic phase is found to stabilize in between the isotropic and smectic A phases only at high temperatures and high densities. The calculated phase diagram is in good qualitative agreement with computer simulation results.