Dynamical Heterogeneity and the interplay between activated and mode coupling dynamics in supercooled liquids

TL;DR

This paper develops a unified theoretical framework combining mode coupling theory and RFOT to analyze the dynamics of supercooled liquids across temperatures, revealing how their interplay affects relaxation and heterogeneity.

Contribution

It introduces a self-consistent theory that integrates MCT and RFOT, capturing the crossover from high-temperature diffusion to low-temperature hopping in supercooled liquids.

Findings

The theory reproduces MCT-like behavior above T_c.

It predicts a crossover from MCT to hopping dominated dynamics below T_c.

Dynamical heterogeneity is enhanced by the interaction between barriers and MCT dynamics.

Abstract

We present a theoretical analysis of the dynamic structure factor (DSF) of a liquid at and below the mode coupling critical temperature $T_c$, by developing a self-consistent theoretical treatment which includes the contributions both from continuous diffusion, described using general two coupling parameter ($F_{12}$) mode coupling theory (MCT), and from the activated hopping, described using the random first order transition (RFOT) theory, incorporating the effect of dynamical heterogeneity. The theory is valid over the whole temperature plane and shows correct limiting MCT like behavior above $T_{c}$ and goes over to the RFOT theory near the glass transition temperature, $T_{g}$. Between $T_{c}$ and $T_{g}$, the theory predicts that neither the continuous diffusion, described by pure mode coupling theory, nor the hopping motion alone suffices but both contribute to the dynamics while interacting with each other. We show that the interplay between the two contributions conspires to modify the relaxation behavior of the DSF from what would be predicted by a theory with a complete static Gaussian barrier distribution in a manner that may be described as a facilitation effect. Close to $T_c$, coupling between the short time part of MCT dynamics and hopping reduces the stretching given by the F$_{12}$-MCT theory significantly and accelerates structural relaxation. As the temperature is progressively lowered below $T_c$, the equations yield a crossover from MCT dominated regime to the hopping dominated regime. In the combined theory the dynamical heterogeneity is modified because the low barrier components interact with the MCT dynamics to enhance the relaxation rate below $T_c$ and reduces the stretching that would otherwise arise from an input static barrier height distribution.