Structural Determination vs Stochastic Events: Relaxation Dynamics in a Supercooled Liquid

Abstract

Structural relaxation in supercooled liquids is influenced by the initial configuration, yet its microscopic evolution exhibits substantial variability. Here, we investigate the interplay between structural constraints and dynamical stochasticity by examining fluctuations of relaxation dynamics across and within isoconfigurational ensembles. We show that fluctuations among trajectories originating from the same configuration constitute a substantial fraction of the total dynamical fluctuations over a broad range of temperatures. At the collective level, the distribution of relaxation times is well described by a stochastic model involving a sequence of effective relaxation events, whose number decreases upon cooling. At the microscopic level, dynamical fluctuations exhibit spatial correlations that grow upon cooling, revealing a spatial organization of relaxation even when the initial configuration is fixed. Remarkably, the characteristic length associated with these fluctuations closely follows the length scale inferred from the stochastic first-passage model, establishing a connection between the spatial organization of dynamical fluctuations and the temporal statistics of collective relaxation. Together, these results suggest that structural relaxation is governed by an interplay between configuration-dependent constraints and stochastic dynamical events: the initial structure influences when and where relaxation occurs, without uniquely determining its microscopic realization.