Correlation between the first-reaction time and the acquired boundary local time

We investigate the statistical correlation between the first-reaction time of a diffusing particle and its boundary local time accumulated until the reaction event. Since the reaction event occurs after multiple encounters of the particle with a partially reactive boundary, the boundary local time as a proxy for the number of such encounters is not independent of, but intrinsically linked to, the first-reaction time. We propose a universal theoretical framework to derive their joint probability density and, in particular, the correlation coefficient. To illustrate the dependence of these correlations on the boundary reactivity and shape, we obtain explicit analytical solutions for several basic domains. The analytical results are complemented by Monte Carlo simulations, which we employ to examine the role of interior obstacles on correlations in disordered media. Applications of these statistical results in chemical physics are discussed.

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Publication Details

Journal
The Journal of Chemical Physics
Published
2026-02-23
DOI
https://doi.org/10.1063/5.0317675
Primary Topic
Diffusion and Search Dynamics
Type
article
Field-Weighted Citation Impact
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article

Correlation between the first-reaction time and the acquired boundary local time

The Journal of Chemical Physics
Diffusion and Search Dynamics
article

Correlation between the first-reaction time and the acquired boundary local time

article en

Abstract

We investigate the statistical correlation between the first-reaction time of a diffusing particle and its boundary local time accumulated until the reaction event. Since the reaction event occurs after multiple encounters of the particle with a partially reactive boundary, the boundary local time as a proxy for the number of such encounters is not independent of, but intrinsically linked to, the first-reaction time. We propose a universal theoretical framework to derive their joint probability density and, in particular, the correlation coefficient. To illustrate the dependence of these correlations on the boundary reactivity and shape, we obtain explicit analytical solutions for several basic domains. The analytical results are complemented by Monte Carlo simulations, which we employ to examine the role of interior obstacles on correlations in disordered media. Applications of these statistical results in chemical physics are discussed.

The Journal of Chemical PhysicsVol. 164(8)
Centre National de la Recherche Scientifique (FR), École Polytechnique (FR)
Openalex Percentile: Top 45%
Diffusion and Search Dynamics
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