A molecular dynamics simulations study on the relations between dynamical heterogeneity, structural relaxation, and self-diffusion in viscous liquids.

We perform molecular dynamics simulations for viscous liquids to study the relations between dynamical heterogeneity, structural (α) relaxation, and self-diffusion. For atomistic models of supercooled water, polymer melts, and an ionic liquid, we characterize the space-time characteristics of dynamical heterogeneity by the degree of deviations from Gaussian displacement statistics (α2), the size of clusters comprising highly mobile particles (S(w)), and the length of strings consisting of cooperatively moving particles (L(w)). Comparison of our findings with previous simulation results for a large variety of viscous liquids, ranging from monoatomic liquids to silica melt, reveals a nearly universal decoupling between the time scales of maximum non-Gaussian parameter (τ(α2)) and the time constant of the α relaxation (τ(α)) upon cooling, explicitly, τ(α2) ∝τ(α)(3/4). Such uniform relation was not observed between the peak times of S(w) or L(w) and τ(α). On the other hand, the temperature-dependent time scale of maximum string length (τ(L)) follows the inverse of the self-diffusion coefficient (D) for various systems at sufficiently low temperatures, i.e., τ(L) ∝ D(-1). These observations are discussed in view of a breakdown of the Stokes-Einstein relation for the studied systems. It is found that the degree of deviation from this relation is correlated with the stretching of the α relaxation.