Accumulation times for diffusion-mediated surface reactions

TL;DR

This paper extends a probabilistic framework for diffusion-mediated surface reactions to multiple particles, analyzing accumulation times and conditions for steady states using boundary local time and Robin boundary value problems.

Contribution

It introduces a multiparticle probabilistic approach and investigates steady state existence and relaxation dynamics through local time moments.

Findings

Existence of non-trivial steady states depends on local time moments.

Accumulation time can be computed from local time statistics.

Finite first two moments of local time are necessary for analysis.

Abstract

In this paper we consider a multiparticle version of a recent probabilistic framework for studying diffusion-mediated surface reactions. The basic idea of the probabilistic approach is to consider the joint probability density or generalized propagator for particle position and the so-called boundary local time. The latter characterizes the amount of time that a Brownian particle spends in the neighborhood of a totally reflecting boundary; the effects of surface reactions are then incorporated via an appropriate stopping condition for the local time. The propagator is determined by solving a Robin boundary value problem, in which the constant rate of reactivity is identified as the Laplace variable $z$ conjugate to the local time, and then inverting the solution with respect to $z$. Here we reinterpret the propagator as a particle concentration in which surface absorption is counterbalanced by particle source terms. We investigate conditions under which there exists a non-trivial steady state solution, and analyze the relaxation to steady state by calculating the corresponding accumulation time. In particular, we show that the first two moments of the stopping local time density have to be finite.