When bigger is faster: a self-van Hove analysis of the enhanced self-diffusion of non-commensurate guest particles in smectics

We investigate the anomalous dynamics in smectic phases of short host rods where, counter-intuitively, long guest rod-shaped particles diffusive faster than the short host ones, due to their precise size mismatch. In addition to the previously reported mean-square displacement, we analyze the time evolution of the Self-van Hove functions G(r,t), as this probability density function uncovers intrinsic heterogeneous dynamics. Through this analysis, we show that the dynamics of the host particles parallel to the director becomes non-gaussian and therefore heterogeneous after the nematic-to-smectic-A phase transition, even though it exhibits a nearly diffusive behavior according to its mean-square displacement. In contrast, the non-commensurate guest particles display Gaussian dynamics of the parallel motion, up to the transition to the smectic-B phase. Thus, we show that the Self-van Hove function is a very sensitive probe to account for the instantaneous and heterogeneous dynamics of our system, and should be more widely considered as a quantitative and complementary approach of the classical mean-square displacement characterization in diffusion processes.
10 pages, 9 figures, the article has been accepted by the Journal of Chemical Physics