Fitzgerald, S orcid.org/0000-0003-2865-3057, Bailey Hass, A, Diaz Leines, G et al. (1 more author) (2023) Stochastic transitions: Paths over higher energy barriers can dominate in the early stages. The Journal of Chemical Physics, 158. 124114. ISSN 0021-9606
Abstract
The time evolution of many physical, chemical, and biological systems can be modelled by stochastic transitions between the minima of the potential energy surface describing the system of interest. We show that in cases where there are two (or more) possible pathways that the system can take, the time available for the transition to occur is crucially important. The well-known results of reaction rate theory for determining the rates of the transitions apply in the long-time limit. However, at short times, the system can instead choose to pass over higher energy barriers with much higher probability, as long as the distance to travel in phase space is shorter. We construct two simple models to illustrate this general phenomenon. We also apply a version of the geometric minimum action method algorithm of Vanden-Eijnden and Heymann [J. Chem. Phys. {\bf 128}, 061103 (2008)] to determine the most likely path at both short and long times.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2023 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). https://doi.org/10.1063/5.0135880 |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Mathematics (Leeds) > Applied Mathematics (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 23 Mar 2023 10:31 |
Last Modified: | 25 Jun 2023 23:17 |
Status: | Published |
Publisher: | American Institute of Physics |
Identification Number: | 10.1063/5.0135880 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:197616 |