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Influence of Vibrational Excitation on the Reaction of F(–) with CH(3)I: Spectator Mode Behavior, Enhancement, and Suppression

[Image: see text] Detailed insight into chemical reaction dynamics can be obtained by probing the effect of mode-specific vibrational excitation. Suppression or enhancement of reactivity is possible as is already known from the Polanyi rules. In the reaction F(–) + CH(3)I, we found vibrational enhan...

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Autores principales: Michaelsen, Tim, Bastian, Björn, Ayasli, Atilay, Strübin, Patrick, Meyer, Jennifer, Wester, Roland
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2020
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7277560/
https://www.ncbi.nlm.nih.gov/pubmed/32383877
http://dx.doi.org/10.1021/acs.jpclett.0c01095
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author Michaelsen, Tim
Bastian, Björn
Ayasli, Atilay
Strübin, Patrick
Meyer, Jennifer
Wester, Roland
author_facet Michaelsen, Tim
Bastian, Björn
Ayasli, Atilay
Strübin, Patrick
Meyer, Jennifer
Wester, Roland
author_sort Michaelsen, Tim
collection PubMed
description [Image: see text] Detailed insight into chemical reaction dynamics can be obtained by probing the effect of mode-specific vibrational excitation. Suppression or enhancement of reactivity is possible as is already known from the Polanyi rules. In the reaction F(–) + CH(3)I, we found vibrational enhancement, suppression, and spectator mode dynamics in the four different reaction channels. For this system we have probed the influence of symmetric CH-stretching vibration over a collision energy range of 0.7–2.3 eV. Proton transfer is significantly enhanced, while for the nucleophilic substitution channel the spectator mode dynamics at lower collision energies unexpectedly move toward enhancement at higher collision energies. In contrast, for two halide abstraction channels, forming FI(–) and FHI(–), we found an overall suppression, which stems mainly from a suppression of the FHI(–) product. We compare these results to quasiclassical trajectory calculations and with the sudden vector projection model.
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spelling pubmed-72775602020-06-15 Influence of Vibrational Excitation on the Reaction of F(–) with CH(3)I: Spectator Mode Behavior, Enhancement, and Suppression Michaelsen, Tim Bastian, Björn Ayasli, Atilay Strübin, Patrick Meyer, Jennifer Wester, Roland J Phys Chem Lett [Image: see text] Detailed insight into chemical reaction dynamics can be obtained by probing the effect of mode-specific vibrational excitation. Suppression or enhancement of reactivity is possible as is already known from the Polanyi rules. In the reaction F(–) + CH(3)I, we found vibrational enhancement, suppression, and spectator mode dynamics in the four different reaction channels. For this system we have probed the influence of symmetric CH-stretching vibration over a collision energy range of 0.7–2.3 eV. Proton transfer is significantly enhanced, while for the nucleophilic substitution channel the spectator mode dynamics at lower collision energies unexpectedly move toward enhancement at higher collision energies. In contrast, for two halide abstraction channels, forming FI(–) and FHI(–), we found an overall suppression, which stems mainly from a suppression of the FHI(–) product. We compare these results to quasiclassical trajectory calculations and with the sudden vector projection model. American Chemical Society 2020-05-08 2020-06-04 /pmc/articles/PMC7277560/ /pubmed/32383877 http://dx.doi.org/10.1021/acs.jpclett.0c01095 Text en Copyright © 2020 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
spellingShingle Michaelsen, Tim
Bastian, Björn
Ayasli, Atilay
Strübin, Patrick
Meyer, Jennifer
Wester, Roland
Influence of Vibrational Excitation on the Reaction of F(–) with CH(3)I: Spectator Mode Behavior, Enhancement, and Suppression
title Influence of Vibrational Excitation on the Reaction of F(–) with CH(3)I: Spectator Mode Behavior, Enhancement, and Suppression
title_full Influence of Vibrational Excitation on the Reaction of F(–) with CH(3)I: Spectator Mode Behavior, Enhancement, and Suppression
title_fullStr Influence of Vibrational Excitation on the Reaction of F(–) with CH(3)I: Spectator Mode Behavior, Enhancement, and Suppression
title_full_unstemmed Influence of Vibrational Excitation on the Reaction of F(–) with CH(3)I: Spectator Mode Behavior, Enhancement, and Suppression
title_short Influence of Vibrational Excitation on the Reaction of F(–) with CH(3)I: Spectator Mode Behavior, Enhancement, and Suppression
title_sort influence of vibrational excitation on the reaction of f(–) with ch(3)i: spectator mode behavior, enhancement, and suppression
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7277560/
https://www.ncbi.nlm.nih.gov/pubmed/32383877
http://dx.doi.org/10.1021/acs.jpclett.0c01095
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