Anomalous tracer diffusion in hard-sphere suspensions

Abstract

Coupled equations describing diffusion and cross-diffusion of tracer particles in hard-sphere suspensions are derived and solved numerically. In concentrated systems with strong excluded volume and viscous interactions the tracer motion is subdiffusive. Cross diffusion generates transient perturbations to the host-particle matrix, which affect the motion of the tracer particles leading to nonlinear mean squared displacements. Above a critical host-matrix concentration the tracers experience clustering and uphill diffusion, moving in opposition to their own concentration gradient. A linear stability analysis indicates that cross diffusion can lead to unstable concentration fluctuations in the suspension. The instability is a potential mechanism for the appearance of dynamic and structural heterogeneity in suspensions near the glass transition.