On the Mechanism of Activated Transport in Glassy Liquids

TL;DR

This paper clarifies the entropic droplet model of activated transport in glassy liquids, showing it is consistent, universal, and matches experimental data, by deriving barrier and length scale expressions from bulk properties.

Contribution

It provides a theoretical validation of the RFOT-based entropic droplet picture, linking activation barriers to bulk moduli and configurational entropy, with predictions aligning with observations.

Findings

Activation barrier expressions depend only on bulk modulus and configurational entropy.

Predicted temperature dependence of barriers agrees with experimental data.

Derived relationships between bulk modulus and glassy liquid properties.

Abstract

We explore several potential issues that have been raised over the years regarding the "entropic droplet" scenario of activated transport in liquids, due to Wolynes and coworkers, with the aim of clarifying the status of various approximations of the random first order transition theory (RFOT) of the structural glass transition. In doing so, we estimate the mismatch penalty between alternative aperiodic structures, above the glass transition; the penalty is equal to the typical magnitude of free energy fluctuations in the liquid. The resulting expressions for the activation barrier and the cooperativity length contain exclusively bulk, static properties; in their simplest form they contains only the bulk modulus and the configurational entropy per unit volume. The expressions are universal in that they do not depend explicitly on the molecular detail. The predicted values for the barrier and cooperativity length and, in particular, the temperature dependence of the barrier are in satisfactory agreement with observation. We thus confirm that the entropic droplet picture is indeed not only internally-consistent but is also fully constructive, consistent with the apparent success of its many quantitative predictions. A simple view of a glassy liquid as a locally metastable, degenerate pattern of frozen-in stress emerges in the present description. Finally, we derive testable relationships between the bulk modulus and several characteristics of glassy liquids and peculiarities in low-temperature glasses.