Smectic order parameters from diffusion data

Microcanonical molecular dynamics simulations have been performed in the smectic A phase of an elementary liquid-crystal model. Smectic order parameters and diffusion coefficients along directions parallel and perpendicular to the director have been calculated during the same trajectory for a number of state points. This has permitted the satisfactory testing of a procedure, adopted in the analysis of experimental self-diffusion coefficients, leading to an estimate of the temperature dependence of the smectic order parameters. This methodology has been then confidently applied to two smectogenic thermotropic liquid crystals belonging to the 4,4(')-di-n-alkyl-azoxybenzene series. The derived smectic order parameters are larger for the homologue compound with the longest alkyl chains. This is consistent with the well-established increased tendency, for members of a homologue series, to form a smectic phase as their alkyl chains become longer.