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Manipulating hydrogen bond dissociation rates and mechanisms in water dimer through vibrational strong coupling

The vibrational strong coupling (VSC) between molecular vibrations and cavity photon modes has recently emerged as a promising tool for influencing chemical reactivities. Despite numerous experimental and theoretical efforts, the underlying mechanism of VSC effects remains elusive. In this study, we...

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Autores principales: Yu, Qi, Bowman, Joel M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10267182/
https://www.ncbi.nlm.nih.gov/pubmed/37316497
http://dx.doi.org/10.1038/s41467-023-39212-y
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author Yu, Qi
Bowman, Joel M.
author_facet Yu, Qi
Bowman, Joel M.
author_sort Yu, Qi
collection PubMed
description The vibrational strong coupling (VSC) between molecular vibrations and cavity photon modes has recently emerged as a promising tool for influencing chemical reactivities. Despite numerous experimental and theoretical efforts, the underlying mechanism of VSC effects remains elusive. In this study, we combine state-of-art quantum cavity vibrational self-consistent field/configuration interaction theory (cav-VSCF/VCI), quasi-classical trajectory method, along with the quantum-chemical CCSD(T)-level machine learning potential, to simulate the hydrogen bond dissociation dynamics of water dimer under VSC. We observe that manipulating the light-matter coupling strength and cavity frequencies can either inhibit or accelerate the dissociation rate. Furthermore, we discover that the cavity surprisingly modifies the vibrational dissociation channels, with a pathway involving both water fragments in their ground vibrational states becoming the major channel, which is a minor one when the water dimer is outside the cavity. We elucidate the mechanisms behind these effects by investigating the critical role of the optical cavity in modifying the intramolecular and intermolecular coupling patterns. While our work focuses on single water dimer system, it provides direct and statistically significant evidence of VSC effects on molecular reaction dynamics.
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spelling pubmed-102671822023-06-15 Manipulating hydrogen bond dissociation rates and mechanisms in water dimer through vibrational strong coupling Yu, Qi Bowman, Joel M. Nat Commun Article The vibrational strong coupling (VSC) between molecular vibrations and cavity photon modes has recently emerged as a promising tool for influencing chemical reactivities. Despite numerous experimental and theoretical efforts, the underlying mechanism of VSC effects remains elusive. In this study, we combine state-of-art quantum cavity vibrational self-consistent field/configuration interaction theory (cav-VSCF/VCI), quasi-classical trajectory method, along with the quantum-chemical CCSD(T)-level machine learning potential, to simulate the hydrogen bond dissociation dynamics of water dimer under VSC. We observe that manipulating the light-matter coupling strength and cavity frequencies can either inhibit or accelerate the dissociation rate. Furthermore, we discover that the cavity surprisingly modifies the vibrational dissociation channels, with a pathway involving both water fragments in their ground vibrational states becoming the major channel, which is a minor one when the water dimer is outside the cavity. We elucidate the mechanisms behind these effects by investigating the critical role of the optical cavity in modifying the intramolecular and intermolecular coupling patterns. While our work focuses on single water dimer system, it provides direct and statistically significant evidence of VSC effects on molecular reaction dynamics. Nature Publishing Group UK 2023-06-14 /pmc/articles/PMC10267182/ /pubmed/37316497 http://dx.doi.org/10.1038/s41467-023-39212-y 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
Yu, Qi
Bowman, Joel M.
Manipulating hydrogen bond dissociation rates and mechanisms in water dimer through vibrational strong coupling
title Manipulating hydrogen bond dissociation rates and mechanisms in water dimer through vibrational strong coupling
title_full Manipulating hydrogen bond dissociation rates and mechanisms in water dimer through vibrational strong coupling
title_fullStr Manipulating hydrogen bond dissociation rates and mechanisms in water dimer through vibrational strong coupling
title_full_unstemmed Manipulating hydrogen bond dissociation rates and mechanisms in water dimer through vibrational strong coupling
title_short Manipulating hydrogen bond dissociation rates and mechanisms in water dimer through vibrational strong coupling
title_sort manipulating hydrogen bond dissociation rates and mechanisms in water dimer through vibrational strong coupling
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10267182/
https://www.ncbi.nlm.nih.gov/pubmed/37316497
http://dx.doi.org/10.1038/s41467-023-39212-y
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