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Direct observation of vibrational energy dispersal: Via methyl torsions

Gardner, Adrian M.; Tuttle, William D.; Whalley, Laura E.; Wright, Timothy G.

Authors

Adrian M. Gardner

William D. Tuttle

Laura E. Whalley

TIMOTHY WRIGHT TIM.WRIGHT@NOTTINGHAM.AC.UK
Professor of Physical and Theoretical Chemistry



Abstract

© 2018 The Royal Society of Chemistry. Explicit evidence for the role of methyl rotor levels in promoting energy dispersal is reported. A set of coupled zero-order vibration/vibration-torsion (vibtor) levels in the S1 state of para-fluorotoluene (pFT) are investigated. Two-dimensional laser-induced fluorescence (2D-LIF) and two-dimensional zero-kinetic-energy (2D-ZEKE) spectra are reported, and the assignment of the main features in both sets of spectra reveals that the methyl torsion is instrumental in providing a route for coupling between vibrational levels of different symmetry classes. We find that there is very localized, and selective, dissipation of energy via doorway states, and that, in addition to an increase in the density of states, a critical role of the methyl group is a relaxation of symmetry constraints compared to direct vibrational coupling.

Citation

Gardner, A. M., Tuttle, W. D., Whalley, L. E., & Wright, T. G. (2018). Direct observation of vibrational energy dispersal: Via methyl torsions. Chemical Science, 9(8), 2270-2283. https://doi.org/10.1039/c7sc05309f

Journal Article Type Article
Acceptance Date Jan 24, 2018
Online Publication Date Jan 24, 2018
Publication Date Jan 1, 2018
Deposit Date Jan 25, 2018
Publicly Available Date Jan 25, 2018
Journal Chemical Science
Print ISSN 2041-6520
Electronic ISSN 2041-6539
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 9
Issue 8
Pages 2270-2283
DOI https://doi.org/10.1039/c7sc05309f
Public URL http://eprints.nottingham.ac.uk/id/eprint/49331
Publisher URL http://pubs.rsc.org/en/Content/ArticleLanding/2018/SC/C7SC05309F#!divAbstract
Copyright Statement Copyright information regarding this work can be found at the following address: http://creativecommons.org/licenses/by/4.0

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Copyright Statement
Copyright information regarding this work can be found at the following address: http://creativecommons.org/licenses/by/4.0





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