Anisotropic medium-range order uncovers dynamic crossovers in glass-forming liquids

Abstract

On cooling liquids towards their glass-transition temperature, the dramatic increase of their relaxation times is accompanied by changes in particle dynamics at two distinct temperatures: A high-T crossover, where particles become temporarily caged by their neighbors, and a low-T crossover, where the cage escape mechanism changes. While there is some evidence that the former is associated with a change in local particle arrangement, no structural modification has so far been detected across the low-T crossover, fueling scepticism about the relevance of structure for glassy dynamics. Here, we introduce a novel four-point correlation function which allows to determine a structural length scale characterizing cage anisotropy. Extensive molecular dynamics simulations reveal that this scale, as well as the mean structural length scale of the glass-former, extends into the medium range, i.e., significantly exceeds the particle size. Strikingly, the difference between these two scales - a measure of the degree of cage anisotropy - peaks at both crossover temperatures. We discuss how the presence of these peaks enables understanding the nature of the change in the microscopic transport mechanism at the two temperatures, thereby linking both dynamical crossovers to a single structural observable, the anisotropic medium-range order. This fundamental insight demonstrates that structure, extending well-beyond the local cage, is an essential ingredient for understanding the relaxation dynamics of deeply supercooled liquids.