Stretching vibration is a spectator in nucleophilic substitution

Martin Stei, Eduardo Carrascosa, Alexander Dörfler, Jennifer Meyer, Balázs Olasz, Gábor Czakó, Anyang Li, Hua Guo, Roland Wester

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

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 CH3I 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.

Original languageEnglish
Article numbereaas9544
JournalScience Advances
Volume4
Issue number7
DOIs
Publication statusPublished - Jul 6 2018

ASJC Scopus subject areas

  • General

Fingerprint Dive into the research topics of 'Stretching vibration is a spectator in nucleophilic substitution'. Together they form a unique fingerprint.

  • Cite this

    Stei, M., Carrascosa, E., Dörfler, A., Meyer, J., Olasz, B., Czakó, G., Li, A., Guo, H., & Wester, R. (2018). Stretching vibration is a spectator in nucleophilic substitution. Science Advances, 4(7), [eaas9544]. https://doi.org/10.1126/sciadv.aas9544