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Effects of symmetry, methyl groups and serendipity on intramolecular vibrational energy dispersal

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

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Authors

William D. Tuttle

Adrian M. Gardner

Laura E. Whalley

David J. Kemp

Timothy G. Wright



Abstract

We consider two key parameters that have been proposed to be important for vibrational energy delocalization, closely related to intramolecular vibrational redistribution (IVR), in molecules. These parameters are the symmetry of the molecule, and the presence of torsional (internal rotor) modes of a methyl group. We consider four para-disubstituted benzene molecules and examine their vibrational character. The molecules selected are para-difluorobenzene, para-chlorofluorobenzene, para-fluorotoluene, and para-xylene. This set of molecules allows the above parameters to be assessed in a systematic way. The probe we use is zero-electron-kinetic-energy (ZEKE) spectroscopy, which is employed in a resonant scheme, where the intermediate levels are selected vibrational levels of the S1 excited electronic state, with wavenumbers up to 1300 cm 1. We conclude that symmetry, and the presence of a methyl groups, do indeed have a profound effect on “restricted” IVR at low energies. This is underpinned by serendipitous coincidences in the energies of the levels, owing to small shifts in vibrational wavenumbers. Additionally, methyl groups play an important role in opening up new routes for coupling between vibrations of different symmetry, and this is critical in the transition to “statistical” IVR at lower energies for molecules that contain them. Further, the presence of two methyl groups in the symmetrically-substituted p-xylene causes more widespread IVR than does the single methyl group in the asymmetrically-substituted p-fluorotoluene.

Citation

Tuttle, W. D., Gardner, A. M., Whalley, L. E., Kemp, D. J., & Wright, T. G. (2019). Effects of symmetry, methyl groups and serendipity on intramolecular vibrational energy dispersal. Physical Chemistry Chemical Physics, 21(26), 14133-14152. https://doi.org/10.1039/C8CP02757A

Journal Article Type Article
Acceptance Date Jun 8, 2018
Online Publication Date Jun 9, 2018
Publication Date Jul 14, 2019
Deposit Date Jun 11, 2018
Publicly Available Date Mar 28, 2024
Journal Physical Chemistry Chemical Physics
Print ISSN 1463-9076
Electronic ISSN 1463-9084
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 21
Issue 26
Pages 14133-14152
DOI https://doi.org/10.1039/C8CP02757A
Public URL https://nottingham-repository.worktribe.com/output/936888
Publisher URL http://pubs.rsc.org/en/content/articlelanding/2018/cp/c8cp02757a#!divAbstract

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