Anomalous diffusion in heterogeneous glass-forming liquids: Temperature-dependent behavior

Abstract

In a preceding paper, Langer and Mukhopadhyay [Phys. Rev. E 77, 061505 (2008)] studied the diffusive motion of a tagged molecule in an heterogeneous glass-forming liquid at temperatures just above a glass transition. Among other features of this system, we postulated a relation between heterogeneity and stretched-exponential decay of correlations, and we also confirmed that systems of this kind generally exhibit non-Gaussian diffusion on intermediate length and time scales. Here I extend this analysis to higher temperatures approaching the point where the heterogeneities disappear and thermal activation barriers become small. I start by modifying the continuous-time random-walk theory proposed in Langer and Mukhopadhyay and supplement this analysis with an extension of the excitation-chain theory of glass dynamics. I also use a key result from the shear-transformation-zone theory of viscous deformation of amorphous materials. Elements of each of these theories are then used to interpret experimental data for orthoterphenyl, specifially, the diffusion and viscosity coefficients and neutron-scattering measurements of the self-intermediate scattering function. Reconciling the theory with these data sets provides insights into the crossover between super-Arrhenius and Arrhenius dynamics, length scales of spatial heterogeneities, violation of the Stokes-Einstein relation in glass-forming liquids, and the origin of stretched-exponential decay of correlations.