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Quantum dynamical effects of vibrational strong coupling in chemical reactivity
Recent experiments suggest that ground state chemical reactivity can be modified when placing molecular systems inside infrared cavities where molecular vibrations are strongly coupled to electromagnetic radiation. This phenomenon lacks a firm theoretical explanation. Here, we employ an exact quantu...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2023
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10182063/ https://www.ncbi.nlm.nih.gov/pubmed/37173299 http://dx.doi.org/10.1038/s41467-023-38368-x |
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author | Lindoy, Lachlan P. Mandal, Arkajit Reichman, David R. |
author_facet | Lindoy, Lachlan P. Mandal, Arkajit Reichman, David R. |
author_sort | Lindoy, Lachlan P. |
collection | PubMed |
description | Recent experiments suggest that ground state chemical reactivity can be modified when placing molecular systems inside infrared cavities where molecular vibrations are strongly coupled to electromagnetic radiation. This phenomenon lacks a firm theoretical explanation. Here, we employ an exact quantum dynamics approach to investigate a model of cavity-modified chemical reactions in the condensed phase. The model contains the coupling of the reaction coordinate to a generic solvent, cavity coupling to either the reaction coordinate or a non-reactive mode, and the coupling of the cavity to lossy modes. Thus, many of the most important features needed for realistic modeling of the cavity modification of chemical reactions are included. We find that when a molecule is coupled to an optical cavity it is essential to treat the problem quantum mechanically to obtain a quantitative account of alterations to reactivity. We find sizable and sharp changes in the rate constant that are associated with quantum mechanical state splittings and resonances. The features that emerge from our simulations are closer to those observed in experiments than are previous calculations, even for realistically small values of coupling and cavity loss. This work highlights the importance of a fully quantum treatment of vibrational polariton chemistry. |
format | Online Article Text |
id | pubmed-10182063 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-101820632023-05-14 Quantum dynamical effects of vibrational strong coupling in chemical reactivity Lindoy, Lachlan P. Mandal, Arkajit Reichman, David R. Nat Commun Article Recent experiments suggest that ground state chemical reactivity can be modified when placing molecular systems inside infrared cavities where molecular vibrations are strongly coupled to electromagnetic radiation. This phenomenon lacks a firm theoretical explanation. Here, we employ an exact quantum dynamics approach to investigate a model of cavity-modified chemical reactions in the condensed phase. The model contains the coupling of the reaction coordinate to a generic solvent, cavity coupling to either the reaction coordinate or a non-reactive mode, and the coupling of the cavity to lossy modes. Thus, many of the most important features needed for realistic modeling of the cavity modification of chemical reactions are included. We find that when a molecule is coupled to an optical cavity it is essential to treat the problem quantum mechanically to obtain a quantitative account of alterations to reactivity. We find sizable and sharp changes in the rate constant that are associated with quantum mechanical state splittings and resonances. The features that emerge from our simulations are closer to those observed in experiments than are previous calculations, even for realistically small values of coupling and cavity loss. This work highlights the importance of a fully quantum treatment of vibrational polariton chemistry. Nature Publishing Group UK 2023-05-12 /pmc/articles/PMC10182063/ /pubmed/37173299 http://dx.doi.org/10.1038/s41467-023-38368-x Text en © The Author(s) 2023 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 Lindoy, Lachlan P. Mandal, Arkajit Reichman, David R. Quantum dynamical effects of vibrational strong coupling in chemical reactivity |
title | Quantum dynamical effects of vibrational strong coupling in chemical reactivity |
title_full | Quantum dynamical effects of vibrational strong coupling in chemical reactivity |
title_fullStr | Quantum dynamical effects of vibrational strong coupling in chemical reactivity |
title_full_unstemmed | Quantum dynamical effects of vibrational strong coupling in chemical reactivity |
title_short | Quantum dynamical effects of vibrational strong coupling in chemical reactivity |
title_sort | quantum dynamical effects of vibrational strong coupling in chemical reactivity |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10182063/ https://www.ncbi.nlm.nih.gov/pubmed/37173299 http://dx.doi.org/10.1038/s41467-023-38368-x |
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