Emergent Facilitation and Glassy Dynamics in Supercooled Liquids

TL;DR

This paper develops a theoretical framework explaining how microscopic excitations and elastic interactions lead to dynamical facilitation and glassy relaxation in supercooled liquids, reproducing key experimental and simulation observations.

Contribution

The authors introduce a theory linking localized bond-exchange events and elastic stresses to emergent facilitation, providing a microscopic understanding of glassy dynamics.

Findings

Reproduces stretched exponential relaxation decay

Captures super-Arrhenius relaxation timescales

Predicts subdiffusive MSD behavior in supercooled liquids

Abstract

In supercooled liquids, dynamical facilitation refers to a phenomenon where microscopic motion begets further motion nearby, resulting in spatially heterogeneous dynamics. This is central to the glassy relaxation dynamics of such liquids, which show super-Arrhenius growth of relaxation timescales with decreasing temperature. Despite the importance of dynamical facilitation, there is no theoretical understanding of how facilitation emerges and impacts relaxation dynamics. Here, we present a theory that explains the microscopic origins of dynamical facilitation. We show that dynamics proceeds by localized bond-exchange events, also known as excitations, resulting in the accumulation of elastic stresses with which new excitations can interact. At low temperatures, these elastic interactions dominate and facilitate the creation of new excitations near prior excitations. Using the theory of linear elasticity and Markov processes, we simulate a model, which reproduces multiple aspects of glassy dynamics observed in experiments and molecular simulations, including the stretched exponential decay of relaxation functions, the super-Arrhenius behavior of relaxation timescales as well as their two-dimensional (2D) finite-size effects. The model also predicts the subdiffusive behavior of the mean squared displacement (MSD) on short, intermediate timescales. Furthermore, we derive the phonon contributions to diffusion and relaxation, which when combined with the excitation contributions produce the two-step relaxation processes, and the ballistic-subdiffusive-diffusive crossover MSD behaviors commonly found in supercooled liquids.