Influence of polydispersity on the relaxation mechanisms of glassy liquids

TL;DR

This study investigates how particle size polydispersity influences the microscopic relaxation mechanisms in glassy liquids, revealing size-dependent dynamics and the importance of considering polydispersity in glass transition studies.

Contribution

It demonstrates the correlation between particle size and mobility, and uncovers size-dependent relaxation behaviors and breakdown of the Stokes-Einstein relation in deeply supercooled liquids.

Findings

Size correlates with particle mobility.

Dynamic separation emerges at the cage escape timescale.

Different particle sizes show varying activation energies.

Abstract

State-of-the-art techniques for simulating deeply supercooled liquids require a high degree of size polydispersity to be effective. While these techniques have enabled great insight into the microscopic dynamics near the glass transition, the effect of the large polydispersity on the dynamics has remained largely unstudied. Here we show that a particle's size not only has a strong correlation with its mobility, but we also observe that, as the mode-coupling temperature is crossed and the system becomes more deeply supercooled, a dynamic separation between small mobile and larger quiescent particles emerges at timescales corresponding to cage escape. Our results suggest that the cage escape of this population of mobile particles facilitates the later structural relaxation of the quiescent particles. In the deep supercooled regime, we show that particles of different sizes display varying degrees of breakdown of the Stokes-Einstein relation and have different activation energy barriers. Overall, this indicates that it is important to account for particle-size effects when generalizing results to other glass-forming systems.