Overdamped van hove function of colloidal suspensions

Abstract

The generalized-hydrodynamic theory for collective diffusion of a monodisperse colloidal suspension is developed in the framework of the Onsager-Machlup theory of time-dependent fluctuations. The time evolution of the intermediate scattering function F(k,t) is derived as a contraction of the description involving the instantaneous particle number concentration, the particle current, and the stress tensor of the Brownian fluid as state variables. We show that the proper overdamped limit of this equation requires the explicit separation of the stress tensor in its mutually orthogonal kinetic and configurational contributions. Analogous results also follow for the self-intermediate scattering function F(s)(k,t). We show that neglecting the non-Markovian part of the configurational stress tensor memory, one recovers the single exponential memory approximation (based on sum rules derived from the Smoluchowski equation) for both F(s)(k,t) and F(k,t). We suggest simple approximate manners to relate the collective and the self-memory functions, leading to Vineyard-like approximate relations between F(s)(k,t) and F(k,t).