Diffusion of rod-like particles in complex fluids

Abstract

Diffusion of particles in complex fluids and gels is difficult to describe and often lies beyond the scope of the classical Stokes-Einstein relation. One of the main lines of research over the past few decades has sought to relate diffusivity to a fundamental dissipative property of the fluid: the wave-vector-dependent shear viscosity function. Here, we use linear response theory to extend this viscosity function framework to rod-like particles. Using a dimer (two-bead particle) as a minimal rod-like probe, we derive explicit expressions for its diffusion coefficients parallel and perpendicular to its axis in terms of the viscosity function. We show that this description captures the full range of behaviors, from nearly isotropic diffusion of the rod-like probe to highly anisotropic, reptation-like motion. The method is based on a microscopic statistical-mechanical treatment of the Smoluchowski dynamics, yet leads to simple final formulas, providing a practical tool for interpreting diffusion experiments on rod-like tracers in complex fluids. We also clarify the limitations of this approach, emphasizing that the present formulation is primarily suited to complex liquids like polymer solutions and only indirectly applicable to gels.