Cargando…
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...
Autores principales: | , , , , , , , , |
---|---|
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 |
_version_ | 1783337983087214592 |
---|---|
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. |
format | Online Article Text |
id | pubmed-6035035 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2018 |
publisher | American Association for the Advancement of Science |
record_format | MEDLINE/PubMed |
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 |
work_keys_str_mv | AT steimartin stretchingvibrationisaspectatorinnucleophilicsubstitution AT carrascosaeduardo stretchingvibrationisaspectatorinnucleophilicsubstitution AT dorfleralexander stretchingvibrationisaspectatorinnucleophilicsubstitution AT meyerjennifer stretchingvibrationisaspectatorinnucleophilicsubstitution AT olaszbalazs stretchingvibrationisaspectatorinnucleophilicsubstitution AT czakogabor stretchingvibrationisaspectatorinnucleophilicsubstitution AT lianyang stretchingvibrationisaspectatorinnucleophilicsubstitution AT guohua stretchingvibrationisaspectatorinnucleophilicsubstitution AT westerroland stretchingvibrationisaspectatorinnucleophilicsubstitution |