Spatially heterogeneous dynamics and locally arrested density fluctuations from first-principles

TL;DR

This paper develops a first-principles formalism based on the Non-Equilibrium Self-Consistent Generalized Langevin Equation theory to describe dynamical heterogeneities and density fluctuations in glass-forming liquids, revealing arrested states and temperature-dependent relaxation behaviors.

Contribution

It introduces a novel diffusion equation incorporating density gradients, mobility factors, and collective effects to analyze heterogeneities in glass-forming liquids from first principles.

Findings

Density profiles can become arrested despite density gradients.

Above a critical temperature, heterogeneities relax to uniformity in finite time.

Relaxation times vary significantly with temperature in concentrated systems.

Abstract

We present a first-principles formalism for studying dynamical heterogeneities in glass forming liquids. Based on the Non-Equilibrium Self-Consistent Generalized Langevin Equation theory, we were able to describe the time-dependent local density profile during the particle interchange among small regions of the fluid. The final form of the diffusion equation contains both, the contribution of the chemical potential gradient written in terms of a coarse-grained density and a collective diffusion coefficient as well as the effect of a history-dependent mobility factor. With this diffusion equation we captured interesting phenomena in glass forming liquids such as the cases when a strong density gradient is accompanied with a very low mobility factor attributable to the denser part: in such circumstances the density profile falls into an arrested state even in the presence of a density gradient. On the other hand, we also show that above a certain critical temperature,which depends on the volume fraction, any density heterogeneity relaxes to a uniform state in a finite time, known as equilibration time. We further show that such equilibration time varies little with the temperature in diluted systems but can change drastically with temperature in concentrated systems.