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Stretching vibration is a spectator in nucleophilic substitution

How chemical reactions are influenced by reactant vibrational excitation is a long-standing question at the core of chemical reaction dynamics. In reactions of polyatomic molecules, where the Polanyi rules are not directly applicable, certain vibrational modes can act as spectators. In nucleophilic...

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Autores principales: Stei, Martin, Carrascosa, Eduardo, Dörfler, Alexander, Meyer, Jennifer, Olasz, Balázs, Czakó, Gábor, Li, Anyang, Guo, Hua, Wester, Roland
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Association for the Advancement of Science 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6035035/
https://www.ncbi.nlm.nih.gov/pubmed/29984305
http://dx.doi.org/10.1126/sciadv.aas9544
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author Stei, Martin
Carrascosa, Eduardo
Dörfler, Alexander
Meyer, Jennifer
Olasz, Balázs
Czakó, Gábor
Li, Anyang
Guo, Hua
Wester, Roland
author_facet Stei, Martin
Carrascosa, Eduardo
Dörfler, Alexander
Meyer, Jennifer
Olasz, Balázs
Czakó, Gábor
Li, Anyang
Guo, Hua
Wester, Roland
author_sort Stei, Martin
collection PubMed
description How chemical reactions are influenced by reactant vibrational excitation is a long-standing question at the core of chemical reaction dynamics. In reactions of polyatomic molecules, where the Polanyi rules are not directly applicable, certain vibrational modes can act as spectators. In nucleophilic substitution reactions, CH stretching vibrations have been considered to be such spectators. While this picture has been challenged by some theoretical studies, experimental insight has been lacking. We show that the nucleophilic substitution reaction of F(−) with CH(3)I is minimally influenced by an excitation of the symmetric CH stretching vibration. This contrasts with the strong vibrational enhancement of the proton transfer reaction measured in parallel. The spectator behavior of the stretching mode is supported by both quasi-classical trajectory simulations and the Sudden Vector Projection model.
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spelling pubmed-60350352018-07-08 Stretching vibration is a spectator in nucleophilic substitution Stei, Martin Carrascosa, Eduardo Dörfler, Alexander Meyer, Jennifer Olasz, Balázs Czakó, Gábor Li, Anyang Guo, Hua Wester, Roland Sci Adv Research Articles How chemical reactions are influenced by reactant vibrational excitation is a long-standing question at the core of chemical reaction dynamics. In reactions of polyatomic molecules, where the Polanyi rules are not directly applicable, certain vibrational modes can act as spectators. In nucleophilic substitution reactions, CH stretching vibrations have been considered to be such spectators. While this picture has been challenged by some theoretical studies, experimental insight has been lacking. We show that the nucleophilic substitution reaction of F(−) with CH(3)I is minimally influenced by an excitation of the symmetric CH stretching vibration. This contrasts with the strong vibrational enhancement of the proton transfer reaction measured in parallel. The spectator behavior of the stretching mode is supported by both quasi-classical trajectory simulations and the Sudden Vector Projection model. American Association for the Advancement of Science 2018-07-06 /pmc/articles/PMC6035035/ /pubmed/29984305 http://dx.doi.org/10.1126/sciadv.aas9544 Text en Copyright © 2018 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
Stei, Martin
Carrascosa, Eduardo
Dörfler, Alexander
Meyer, Jennifer
Olasz, Balázs
Czakó, Gábor
Li, Anyang
Guo, Hua
Wester, Roland
Stretching vibration is a spectator in nucleophilic substitution
title Stretching vibration is a spectator in nucleophilic substitution
title_full Stretching vibration is a spectator in nucleophilic substitution
title_fullStr Stretching vibration is a spectator in nucleophilic substitution
title_full_unstemmed Stretching vibration is a spectator in nucleophilic substitution
title_short Stretching vibration is a spectator in nucleophilic substitution
title_sort stretching vibration is a spectator in nucleophilic substitution
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6035035/
https://www.ncbi.nlm.nih.gov/pubmed/29984305
http://dx.doi.org/10.1126/sciadv.aas9544
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