The Origin of Persistent Shear Stress in Supercooled Liquids

TL;DR

This paper investigates the origin of persistent shear stress in supercooled liquids, linking it to residual stresses in local potential minima and identifying a mechanical transition above the glass transition temperature.

Contribution

It reveals that the long-time tail of shear stress autocorrelation arises from residual stresses in local minima and identifies a crossover temperature for stress relaxation mechanisms.

Findings

Residual shear stress in local minima causes long-time stress autocorrelation tail.

A mechanical transition occurs above the glass transition temperature.

Decreasing density disrupts the ability of minima to sustain persistent stress.

Abstract

We show that the long time tail of the shear stress autocorrelation, whose growth at large supercooling is responsible for the apparent divergence of the shear viscosity, is a direct result of a residual shear stress in the structures associated with the local potential minima. We argue that the essential mechanical transition experienced by a liquid on cooling occurs at a temperature well above the glass transition temperature and corresponds to the crossover from the high temperature liquid to the viscous liquid, the latter characterised by stress relaxation dominated by the residual stress. Following on from this observation, as the density is decreased, the local potential minima become unable to sustain any persistent stress (and, hence, support a glass transition), in a manner that can be explicitly connected to the interactions between atoms. The reported crossover implies an associated change in the mechanism of dissipation in liquids and, hence, raises the prospect of a coherent microscopic treatment of nonlinear rheology and the relationship between self diffusion and viscosity in supercooled liquids.