Volume 2, Issue 3
Hamilton Dynamics in Chemical Reactions: The Maupertuis Principle, Transition Paths and Energy Landscape

Yuan Gao & Yufan Zhou

Commun. Math. Anal. Appl., 2 (2023), pp. 245-288.

Published online: 2023-09

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  • Abstract

In this paper, we explore the Hamilton structures in non-equilibrium chemical reactions, which is modeled as a random time-changed Poisson process on countable states. Transition paths between multiple steady states in a chemical reaction is a rare event that can be characterized via the large deviation principle. Compared with the Hamilton principle, we use the Maupertuis principle to compute the transition paths and the associated energy barriers, i.e., the rate function in the large deviation principle. Based on the corresponding stationary Hamilton-Jacobi equation, we select a proper stationary viscosity solution, which in general is not unique, to explicitly compute the energy barriers and the associated optimal control that realizes a transition path. Using one-dimensional example, we characterize the energy barriers for chemical reactions using a geometric quantity in the phase plane. We also compare the reaction barriers with the one in the diffusion approximation and show that the global energy landscape and energy barriers for non-equilibrium chemical reactions are quite different with its diffusion approximation.

  • AMS Subject Headings

49L99, 80A30, 49N99

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COPYRIGHT: © Global Science Press

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@Article{CMAA-2-245, author = {Gao , Yuan and Zhou , Yufan}, title = {Hamilton Dynamics in Chemical Reactions: The Maupertuis Principle, Transition Paths and Energy Landscape}, journal = {Communications in Mathematical Analysis and Applications}, year = {2023}, volume = {2}, number = {3}, pages = {245--288}, abstract = {

In this paper, we explore the Hamilton structures in non-equilibrium chemical reactions, which is modeled as a random time-changed Poisson process on countable states. Transition paths between multiple steady states in a chemical reaction is a rare event that can be characterized via the large deviation principle. Compared with the Hamilton principle, we use the Maupertuis principle to compute the transition paths and the associated energy barriers, i.e., the rate function in the large deviation principle. Based on the corresponding stationary Hamilton-Jacobi equation, we select a proper stationary viscosity solution, which in general is not unique, to explicitly compute the energy barriers and the associated optimal control that realizes a transition path. Using one-dimensional example, we characterize the energy barriers for chemical reactions using a geometric quantity in the phase plane. We also compare the reaction barriers with the one in the diffusion approximation and show that the global energy landscape and energy barriers for non-equilibrium chemical reactions are quite different with its diffusion approximation.

}, issn = {2790-1939}, doi = {https://doi.org/10.4208/cmaa.2023-0003}, url = {http://global-sci.org/intro/article_detail/cmaa/22014.html} }
TY - JOUR T1 - Hamilton Dynamics in Chemical Reactions: The Maupertuis Principle, Transition Paths and Energy Landscape AU - Gao , Yuan AU - Zhou , Yufan JO - Communications in Mathematical Analysis and Applications VL - 3 SP - 245 EP - 288 PY - 2023 DA - 2023/09 SN - 2 DO - http://doi.org/10.4208/cmaa.2023-0003 UR - https://global-sci.org/intro/article_detail/cmaa/22014.html KW - Large deviation principle, thermodynamic limit, transition time, energy barriers, infinite time horizon. AB -

In this paper, we explore the Hamilton structures in non-equilibrium chemical reactions, which is modeled as a random time-changed Poisson process on countable states. Transition paths between multiple steady states in a chemical reaction is a rare event that can be characterized via the large deviation principle. Compared with the Hamilton principle, we use the Maupertuis principle to compute the transition paths and the associated energy barriers, i.e., the rate function in the large deviation principle. Based on the corresponding stationary Hamilton-Jacobi equation, we select a proper stationary viscosity solution, which in general is not unique, to explicitly compute the energy barriers and the associated optimal control that realizes a transition path. Using one-dimensional example, we characterize the energy barriers for chemical reactions using a geometric quantity in the phase plane. We also compare the reaction barriers with the one in the diffusion approximation and show that the global energy landscape and energy barriers for non-equilibrium chemical reactions are quite different with its diffusion approximation.

Yuan Gao & Yufan Zhou. (2023). Hamilton Dynamics in Chemical Reactions: The Maupertuis Principle, Transition Paths and Energy Landscape. Communications in Mathematical Analysis and Applications. 2 (3). 245-288. doi:10.4208/cmaa.2023-0003
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