Studies of translational diffusion in the smectic A phase of a Gay-Berne mesogen using molecular dynamics computer simulation.

Molecular dynamics computer simulations are used to determine the self-diffusion coefficients for a Gay-Berne model mesogen GB (4.4,20,1,1) in the isotropic, nematic and smectic A phases along two isobars. The values of the parallel and perpendicular diffusion coefficients, D(parallel) and D(perpendicular), are calculated and compared in the different phases. For the phase sequence isotropic-smectic A, D(perpendicular)> or =D(parallel) over the whole smectic A range with the ratio D(parallel)/D(perpendicular) decreasing with decreasing temperature. At a higher pressure, a nematic phase is observed between these two phases and we find that D(parallel)>D(perpendicular) throughout the nematic region and the inequality D(parallel)>D(perpendicular) remains on entering the smectic A phase. However, the ratio D(parallel)/D(perpendicular) decreases with decreasing temperature within the smectic A range and eventually this ratio inverts such that D(perpendicular)>D(parallel) at low temperatures. The temperature dependence of the parallel diffusion coefficient in the smectic A phase for this model mesogen is compared to that predicted by a theoretical model for diffusion subject to a cosine potential.