Local-Average Free Volume Correlates with Dynamics in Glass Formers.

Abstract

Glass formers exhibit a pronounced slowdown in dynamics, accompanied by progressive heterogeneity as they approach the glass transition. There is intense debate over whether the dramatic slowdown is caused by dynamical heterogeneity and whether the enhanced dynamical heterogeneity originates from structural causes. However, the connection between dynamical heterogeneity and the spatial distribution of the single-particle free volume (a purely static structural quantity) was found to be rather weak, which raises the question of whether dynamic heterogeneity has a purely structural origin. Here, by introducing the concept of local-average free volume, we present numerical evidence that long-time dynamic heterogeneity shows significantly enhanced correlation with the average local free volume over a length scale of a few neighboring shells. Our results resolve the long-standing controversy about whether free volume plays an important role in particle rearrangements associated with the activated hopping relaxation. The concept of "local average" can be applied to other local structural descriptors to better correlate with dynamic heterogeneity in glass-forming liquids.