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Universal kinetics of imperfect reactions in confinement

Chemical reactions generically require that particles come into contact. In practice, reaction is often imperfect and can necessitate multiple random encounters between reactants. In confined geometries, despite notable recent advances, there is to date no general analytical treatment of such imperf...

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Autores principales: Guérin, Thomas, Dolgushev, Maxim, Bénichou, Olivier, Voituriez, Raphaël
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814865/
https://www.ncbi.nlm.nih.gov/pubmed/36697538
http://dx.doi.org/10.1038/s42004-021-00591-2
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author Guérin, Thomas
Dolgushev, Maxim
Bénichou, Olivier
Voituriez, Raphaël
author_facet Guérin, Thomas
Dolgushev, Maxim
Bénichou, Olivier
Voituriez, Raphaël
author_sort Guérin, Thomas
collection PubMed
description Chemical reactions generically require that particles come into contact. In practice, reaction is often imperfect and can necessitate multiple random encounters between reactants. In confined geometries, despite notable recent advances, there is to date no general analytical treatment of such imperfect transport-limited reaction kinetics. Here, we determine the kinetics of imperfect reactions in confining domains for any diffusive or anomalously diffusive Markovian transport process, and for different models of imperfect reactivity. We show that the full distribution of reaction times is obtained in the large confining volume limit from the knowledge of the mean reaction time only, which we determine explicitly. This distribution for imperfect reactions is found to be identical to that of perfect reactions upon an appropriate rescaling of parameters, which highlights the robustness of our results. Strikingly, this holds true even in the regime of low reactivity where the mean reaction time is independent of the transport process, and can lead to large fluctuations of the reaction time - even in simple reaction schemes. We illustrate our results for normal diffusion in domains of generic shape, and for anomalous diffusion in complex environments, where our predictions are confirmed by numerical simulations.
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spelling pubmed-98148652023-01-10 Universal kinetics of imperfect reactions in confinement Guérin, Thomas Dolgushev, Maxim Bénichou, Olivier Voituriez, Raphaël Commun Chem Article Chemical reactions generically require that particles come into contact. In practice, reaction is often imperfect and can necessitate multiple random encounters between reactants. In confined geometries, despite notable recent advances, there is to date no general analytical treatment of such imperfect transport-limited reaction kinetics. Here, we determine the kinetics of imperfect reactions in confining domains for any diffusive or anomalously diffusive Markovian transport process, and for different models of imperfect reactivity. We show that the full distribution of reaction times is obtained in the large confining volume limit from the knowledge of the mean reaction time only, which we determine explicitly. This distribution for imperfect reactions is found to be identical to that of perfect reactions upon an appropriate rescaling of parameters, which highlights the robustness of our results. Strikingly, this holds true even in the regime of low reactivity where the mean reaction time is independent of the transport process, and can lead to large fluctuations of the reaction time - even in simple reaction schemes. We illustrate our results for normal diffusion in domains of generic shape, and for anomalous diffusion in complex environments, where our predictions are confirmed by numerical simulations. Nature Publishing Group UK 2021-11-11 /pmc/articles/PMC9814865/ /pubmed/36697538 http://dx.doi.org/10.1038/s42004-021-00591-2 Text en © The Author(s) 2021 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Guérin, Thomas
Dolgushev, Maxim
Bénichou, Olivier
Voituriez, Raphaël
Universal kinetics of imperfect reactions in confinement
title Universal kinetics of imperfect reactions in confinement
title_full Universal kinetics of imperfect reactions in confinement
title_fullStr Universal kinetics of imperfect reactions in confinement
title_full_unstemmed Universal kinetics of imperfect reactions in confinement
title_short Universal kinetics of imperfect reactions in confinement
title_sort universal kinetics of imperfect reactions in confinement
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814865/
https://www.ncbi.nlm.nih.gov/pubmed/36697538
http://dx.doi.org/10.1038/s42004-021-00591-2
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