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Conical intersection–regulated intermediates in bimolecular reactions: Insights from C((1)D) + HD dynamics
The importance of conical intersections (CIs) in electronically nonadiabatic processes is well known, but their influence on adiabatic dynamics has been underestimated. Here, through combined experimental and theoretical studies, we show that CIs induce a barrier and regulate conversion from a precu...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Association for the Advancement of Science
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6486230/ https://www.ncbi.nlm.nih.gov/pubmed/31032418 http://dx.doi.org/10.1126/sciadv.aaw0446 |
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author | Wu, Yanan Cao, Jianwei Ma, Haitao Zhang, Chunfang Bian, Wensheng Nunez-Reyes, Dianailys Hickson, Kevin M. |
author_facet | Wu, Yanan Cao, Jianwei Ma, Haitao Zhang, Chunfang Bian, Wensheng Nunez-Reyes, Dianailys Hickson, Kevin M. |
author_sort | Wu, Yanan |
collection | PubMed |
description | The importance of conical intersections (CIs) in electronically nonadiabatic processes is well known, but their influence on adiabatic dynamics has been underestimated. Here, through combined experimental and theoretical studies, we show that CIs induce a barrier and regulate conversion from a precursor metastable intermediate (CI-R) to a deep well one. This results in bond-selective activation, influencing the adiabatic dynamics markedly in the C((1)D) + HD reaction. Theory is validated by experiment; quantum dynamics calculations on highly accurate ab initio potential energy surfaces yield rate coefficients and product branching ratios in excellent agreement with the experiment. Quasi-classical trajectory calculations reveal that the CI-R intermediate leads to unusual reaction mechanisms (designated as C─H activation complex conversion and cyclic complex), which are responsible for large branching ratios. We also reveal that CI-R intermediates exist in other reactive systems, and the dynamical effects uncovered here may have general significance. |
format | Online Article Text |
id | pubmed-6486230 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | American Association for the Advancement of Science |
record_format | MEDLINE/PubMed |
spelling | pubmed-64862302019-04-27 Conical intersection–regulated intermediates in bimolecular reactions: Insights from C((1)D) + HD dynamics Wu, Yanan Cao, Jianwei Ma, Haitao Zhang, Chunfang Bian, Wensheng Nunez-Reyes, Dianailys Hickson, Kevin M. Sci Adv Research Articles The importance of conical intersections (CIs) in electronically nonadiabatic processes is well known, but their influence on adiabatic dynamics has been underestimated. Here, through combined experimental and theoretical studies, we show that CIs induce a barrier and regulate conversion from a precursor metastable intermediate (CI-R) to a deep well one. This results in bond-selective activation, influencing the adiabatic dynamics markedly in the C((1)D) + HD reaction. Theory is validated by experiment; quantum dynamics calculations on highly accurate ab initio potential energy surfaces yield rate coefficients and product branching ratios in excellent agreement with the experiment. Quasi-classical trajectory calculations reveal that the CI-R intermediate leads to unusual reaction mechanisms (designated as C─H activation complex conversion and cyclic complex), which are responsible for large branching ratios. We also reveal that CI-R intermediates exist in other reactive systems, and the dynamical effects uncovered here may have general significance. American Association for the Advancement of Science 2019-04-26 /pmc/articles/PMC6486230/ /pubmed/31032418 http://dx.doi.org/10.1126/sciadv.aaw0446 Text en Copyright © 2019 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC). http://creativecommons.org/licenses/by-nc/4.0/ This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license (http://creativecommons.org/licenses/by-nc/4.0/) , which permits use, distribution, and reproduction in any medium, so long as the resultant use is not for commercial advantage and provided the original work is properly cited. |
spellingShingle | Research Articles Wu, Yanan Cao, Jianwei Ma, Haitao Zhang, Chunfang Bian, Wensheng Nunez-Reyes, Dianailys Hickson, Kevin M. Conical intersection–regulated intermediates in bimolecular reactions: Insights from C((1)D) + HD dynamics |
title | Conical intersection–regulated intermediates in bimolecular reactions: Insights from C((1)D) + HD dynamics |
title_full | Conical intersection–regulated intermediates in bimolecular reactions: Insights from C((1)D) + HD dynamics |
title_fullStr | Conical intersection–regulated intermediates in bimolecular reactions: Insights from C((1)D) + HD dynamics |
title_full_unstemmed | Conical intersection–regulated intermediates in bimolecular reactions: Insights from C((1)D) + HD dynamics |
title_short | Conical intersection–regulated intermediates in bimolecular reactions: Insights from C((1)D) + HD dynamics |
title_sort | conical intersection–regulated intermediates in bimolecular reactions: insights from c((1)d) + hd dynamics |
topic | Research Articles |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6486230/ https://www.ncbi.nlm.nih.gov/pubmed/31032418 http://dx.doi.org/10.1126/sciadv.aaw0446 |
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