Heterogeneous Diffusion in Highly Supercooled Liquids

Abstract

The diffusivity of tagged particles is demonstrated to be very heterogeneous on time scales comparable to or shorter than the $\alpha$ relaxation time $\tau_{\alpha}$ ($\cong$ the stress relaxation time) in a highly supercooled liquid via 3D molecular dynamics simulation. The particle motions in the relatively active regions dominantly contribute to the mean square displacement, giving rise to a diffusion constant systematically larger than the Einstein-Stokes value. The van Hove self-correlation function $G_s(r,t)$ is shown to have a long distance tail which can be scaled in terms of $r/t^{1/2}$ for $t \ls 3\tau_{\alpha}$. Its presence indicates heterogeneous diffusion in the active regions. However, the diffusion process eventually becomes homogeneous on time scales longer than the life time of the heterogeneity structure ($\sim 3 \tau_{\alpha}$).