Universal divergenceless scaling between structural relaxation and caged dynamics in glass-forming systems

TL;DR

This study uncovers a universal, divergenceless scaling law linking structural relaxation times and caged dynamics in glass-formers, supported by simulations and experiments across a wide range of conditions.

Contribution

It introduces a new analytic model describing the scaling between relaxation time and cage dynamics without assuming divergence, validated by extensive simulations and experimental data.

Findings

Scaling between relaxation time and Debye-Waller factor is universal.

The model fits data over eighteen orders of magnitude in relaxation times.

Results align with Lindemann melting criterion and free-volume concepts.

Abstract

On approaching the glass transition, the microscopic kinetic unit spends increasing time rattling in the cage of the first neighbours whereas its average escape time, the structural relaxation time $\tau_\alpha$, increases from a few picoseconds up to thousands of seconds. A thorough study of the correlation between $\tau_\alpha$ and the rattling amplitude, expressed by the Debye-Waller factor (DW), was carried out. Molecular-dynamics (MD) simulations of both a model polymer system and a binary mixture were performed by varying the temperature, the density $\rho$, the potential and the polymer length to consider the structural relaxation as well as both the rotational and the translation diffusion. The simulations evidence the scaling between the $\tau_\alpha$ and the Debye-Waller factor. An analytic model of the master curve is developed in terms of two characteristic length scales pertaining to the distance to be covered by the kinetic unit to reach a transition state. The model does not imply $\tau_\alpha$ divergences. The comparison with the experiments supports the numerical evidence over a range of relaxation times as wide as about eighteen orders of magnitude. A comparison with other scaling and correlation procedures is presented. The study suggests that the equilibrium and the moderately supercooled states of the glassformers possess key information on the huge slowing-down of their relaxation close to the glass transition. The latter, according to the present simulations, exhibits features consistent with the Lindemann melting criterion and the free-volume model.