Role of structure in the alpha and beta dynamics of a simple glass-forming liquid

TL;DR

This study uses molecular dynamics simulations to explore how local structure influences the alpha and beta relaxation processes in a simple glass-forming liquid, revealing that structure predominantly controls beta relaxation.

Contribution

It demonstrates that local structural arrangements govern beta relaxation independently of alpha dynamics in a simple, two-dimensional molecular model.

Findings

Beta and alpha relaxations are correlated in average properties but not at the single-molecule level.

Long-time mobility heterogeneity is observed at both relaxation timescales.

Local structure is the dominant factor controlling beta relaxation, especially in the glassy state.

Abstract

The elusive connection between dynamics and local structure in supercooled liquids is an important piece of the puzzle in the unsolved problem of the glass transition. The Johari-Goldstein beta relaxation, ubiquitous in glass-forming liquids, exhibits mean properties that are strongly correlated to the long-time alpha dynamics. However, the former comprises simpler, more localized motion, and thus has perhaps a more straightforward connection to structure. Molecular dynamics simulations were carried out on a two-dimensional, rigid diatomic molecule (the simplest structure exhibiting a distinct beta process) to assess the role of the local liquid structure on both the Johari-Goldstein beta and the alpha relaxation. Although the average properties for these two relaxations are correlated, there is no connection between the beta and alpha properties of a given (single) molecule. The propensity for motion at long times is independent of the rate or strength of a molecule's beta relaxation. The mobility of a molecule averaged over many initial energies, a measure of the influence of structure, was found to be heterogeneous, with clustering at both the beta and alpha timescales. This heterogeneity is less extended spatially for the beta than for the alpha dynamics, as expected; however, the local structure is the more dominant control parameter for the beta prcoess. In the glassy state, the arrangement of neighboring molecules determines entirely the relaxation properties, with no discernible effect from the particle momenta.