Length scale for the onset of Fickian diffusion in supercooled liquids

TL;DR

This paper identifies a dynamic length scale in supercooled liquids that marks the onset of Fickian diffusion breakdown, linking microscopic dynamics to macroscopic transport properties across different temperatures.

Contribution

It introduces a specific length scale for Fickian diffusion onset and analyzes its temperature dependence in various fragile liquids, supported by analytical estimates.

Findings

A dynamic length scale exists for Fickian diffusion breakdown.

The length scale's temperature dependence varies with liquid fragility.

Analytical estimates for scattering functions are provided.

Abstract

The interplay between self-diffusion and excitation lines in space-time was recently studied in kinetically constrained models to explain the breakdown of the Stokes-Einstein law in supercooled liquids. Here, we further examine this interplay and its manifestation in incoherent scattering functions. In particular, we establish a dynamic length scale below which Fickian diffusion breaks down, as is observed in experiments and simulations. We describe the temperature dependence of this length scale in liquids of various fragilities, and provide analytical estimates for the van Hove and self-intermediate scattering functions.