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Stable chaos and delayed onset of statisticality in unimolecular dissociation reactions
Statistical models provide a powerful and useful class of approximations for calculating reaction rates by bypassing the need for detailed, and often difficult, dynamical considerations. Such approaches invariably invoke specific assumptions about the extent of intramolecular vibrational energy flow...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814671/ https://www.ncbi.nlm.nih.gov/pubmed/36703308 http://dx.doi.org/10.1038/s42004-019-0252-y |
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author | Karmakar, Sourav Yadav, Pankaj Kumar Keshavamurthy, Srihari |
author_facet | Karmakar, Sourav Yadav, Pankaj Kumar Keshavamurthy, Srihari |
author_sort | Karmakar, Sourav |
collection | PubMed |
description | Statistical models provide a powerful and useful class of approximations for calculating reaction rates by bypassing the need for detailed, and often difficult, dynamical considerations. Such approaches invariably invoke specific assumptions about the extent of intramolecular vibrational energy flow in the system. However, the nature of the transition to the statistical regime as a function of the molecular parameters is far from being completely understood. Here, we use tools from nonlinear dynamics to study the transition to statisticality in a model unimolecular reaction by explicitly visualizing the high dimensional classical phase space. We identify generic features in the phase space involving the intersection of two or more independent anharmonic resonances and show that the presence of correlated, but chaotic, intramolecular dynamics near such junctions leads to nonstatisticality. Interestingly, akin to the stability of asteroids in the Solar System, molecules can stay protected from dissociation at the junctions for several picoseconds due to the phenomenon of stable chaos. |
format | Online Article Text |
id | pubmed-9814671 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-98146712023-01-10 Stable chaos and delayed onset of statisticality in unimolecular dissociation reactions Karmakar, Sourav Yadav, Pankaj Kumar Keshavamurthy, Srihari Commun Chem Article Statistical models provide a powerful and useful class of approximations for calculating reaction rates by bypassing the need for detailed, and often difficult, dynamical considerations. Such approaches invariably invoke specific assumptions about the extent of intramolecular vibrational energy flow in the system. However, the nature of the transition to the statistical regime as a function of the molecular parameters is far from being completely understood. Here, we use tools from nonlinear dynamics to study the transition to statisticality in a model unimolecular reaction by explicitly visualizing the high dimensional classical phase space. We identify generic features in the phase space involving the intersection of two or more independent anharmonic resonances and show that the presence of correlated, but chaotic, intramolecular dynamics near such junctions leads to nonstatisticality. Interestingly, akin to the stability of asteroids in the Solar System, molecules can stay protected from dissociation at the junctions for several picoseconds due to the phenomenon of stable chaos. Nature Publishing Group UK 2020-01-08 /pmc/articles/PMC9814671/ /pubmed/36703308 http://dx.doi.org/10.1038/s42004-019-0252-y Text en © The Author(s) 2020 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 Karmakar, Sourav Yadav, Pankaj Kumar Keshavamurthy, Srihari Stable chaos and delayed onset of statisticality in unimolecular dissociation reactions |
title | Stable chaos and delayed onset of statisticality in unimolecular dissociation reactions |
title_full | Stable chaos and delayed onset of statisticality in unimolecular dissociation reactions |
title_fullStr | Stable chaos and delayed onset of statisticality in unimolecular dissociation reactions |
title_full_unstemmed | Stable chaos and delayed onset of statisticality in unimolecular dissociation reactions |
title_short | Stable chaos and delayed onset of statisticality in unimolecular dissociation reactions |
title_sort | stable chaos and delayed onset of statisticality in unimolecular dissociation reactions |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814671/ https://www.ncbi.nlm.nih.gov/pubmed/36703308 http://dx.doi.org/10.1038/s42004-019-0252-y |
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