Brownian motion at various length scales with hydrodynamic and direct interactions

TL;DR

This paper investigates Brownian motion in complex liquids across different length scales, emphasizing the role of wave-vector-dependent viscosity and hydrodynamic interactions, offering a new microscopic theoretical framework for diffusion analysis.

Contribution

It introduces a systematic microscopic approach to analyze self-diffusion of probes in complex liquids considering hydrodynamic effects at multiple scales.

Findings

Wave-vector-dependent viscosity encodes multiscale hydrodynamics.

Exact expressions for diffusion coefficients are derived.

The theory highlights limits for small and large probe sizes.

Abstract

Brownian motion is essential for describing diffusion in systems ranging from simple to complex liquids. Unlike simple liquids, which consist of only a solvent, complex liquids, such as colloidal suspensions or the cytoplasm of a cell, are mixtures of various constituents with different shapes and sizes. Describing Brownian motion in such multiscale systems is extremely challenging because direct and many-body hydrodynamic interactions (and their interplay) play a pivotal role. Diffusion of small particles is mainly governed by a low viscous character of the solution, whereas large particles experience a highly viscous flow of the complex liquid on the macro scale. A quantity that encodes hydrodynamics on both length scales is the wave-vector-dependent viscosity. Assuming this quantity to be known -- in contrast to most studies in which the solvent shear viscosity is given -- provides a new perspective on studying the diffusivity of a tracer, especially in situations where the tracer size can vary by several orders of magnitude. Here, we start systematic studies of exact formal microscopic expressions for the short- and long-time self-diffusion coefficients of a single probe particle in a complex liquid in terms of short-ranged hydrodynamic response kernels. We study Brownian motion as a function of the probe size, contrasting most theories that focus on self-diffusion as a function of the crowder volume fraction. We discuss the limits of small and large probe sizes for various levels of approximations in our theory, and discuss the current successes and shortcomings of our approach.