How stickiness can speed up diffusion in confined systems

TL;DR

This paper demonstrates that making surfaces attractive in confined diffusion systems can accelerate particle dispersion, even when surface diffusion is slower than in the bulk, challenging traditional views on crowding effects.

Contribution

It introduces an analytical framework showing how surface attraction can enhance diffusion in confined media, supported by formulas, simulations, and numerical calculations.

Findings

Attractive surfaces can speed up diffusion despite slower surface diffusion.

Enhancement occurs even when surface diffusion is less than bulk diffusion.

Analytical formulas are provided for periodic spheres and undulating channels.

Abstract

The paradigmatic model for heterogeneous media used in diffusion studies is built from reflecting obstacles and surfaces. It is well known that the crowding effect produced by these reflecting surfaces slows the dispersion of Brownian tracers. Here, using a general adsorption desorption model with surface diffusion, we show analytically that making surfaces or obstacles attractive can accelerate dispersion. In particular, we show that this enhancement of diffusion can exist even when the surface diffusion constant is smaller than that in the bulk. Even more remarkably, this enhancement effect occurs when the effective diffusion constant, when restricted to surfaces only, is lower than the effective diffusivity with purely reflecting boundaries. We give analytical formulas for this intriguing effect in periodic arrays of spheres as well as undulating micro-channels. Our results are confirmed by numerical calculations and Monte Carlo simulations.