Direct observation of vibrational energy dispersal via methyl torsions

Gardner, Adrian M., Tuttle, William D., Whalley, Laura E. and Wright, Timothy G. (2018) Direct observation of vibrational energy dispersal via methyl torsions. Chemical Science . ISSN 2041-6520

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Abstract

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.

Item Type: Article
RIS ID: https://nottingham-repository.worktribe.com/output/906830
Schools/Departments: University of Nottingham, UK > Faculty of Science > School of Chemistry
Identification Number: https://doi.org/10.1039/C7SC05309F
Depositing User: Smith, Ruth
Date Deposited: 25 Jan 2018 14:11
Last Modified: 04 May 2020 19:28
URI: https://eprints.nottingham.ac.uk/id/eprint/49331

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