Effects of inhomogeneous partial absorption and the geometry of the boundary on the population evolution of molecules diffusing in general porous media

TL;DR

This paper investigates how inhomogeneous boundary absorption and pore geometry influence the population dynamics of diffusing molecules in porous media, revealing complex interactions that affect relaxation spectra.

Contribution

It introduces a perturbative approach to analyze the effects of spatially varying boundary conditions on diffusion spectra in porous structures.

Findings

Inhomogeneous boundary conditions significantly alter the relaxation spectrum.

The method provides bounds for changes in the slowest relaxation mode.

Numerical simulations confirm the theoretical predictions.

Abstract

We consider aspects of the population dynamics, inside a bound domain, of diffusing agents carrying an attribute which is stochastically destroyed upon contact with the boundary. The normal mode analysis of the relevant Helmholtz equation under the partially absorbing, but uniform, boundary condition provides a starting framework in understanding detailed evolution dynamics of the attribute in the time domain. In particular, the boundary-localized depletion has been widely employed in practical applications that depend on geometry of various porous media such as rocks, cement, bones, and cheese. While direct relationship between the pore geometry and the diffusion-relaxation spectrum forms the basis for such applications and has been extensively studied, relatively less attention has been paid to the spatial variation of the boundary condition. In this work, we focus on the way the pore geometry and the inhomogeneous depletion strength of the boundary become intertwined and thus obscure the direct relationship between the spectrum and the geometry. It is often impossible to gauge experimentally the degree to which such interference occur. We fill this gap by perturbatively incorporating classes of spatially-varying boundary conditions and derive their consequences that are observable through numerical simulations or controlled experiments on glass bead packs and artificially fabricated porous media. We identify features of the spectrum that are most sensitive to the inhomogeneity and apply the method to the spherical pore with a simple hemi-spherical binary distribution of the depletion strength and obtain bounds for the induced change in the slowest relaxation mode.