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Issue 8, 2018
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Direct observation of vibrational energy dispersal via methyl torsions

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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.

Graphical abstract: Direct observation of vibrational energy dispersal via methyl torsions

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Publication details

The article was received on 14 Dec 2017, accepted on 24 Jan 2018 and first published on 24 Jan 2018


Article type: Edge Article
DOI: 10.1039/C7SC05309F
Citation: Chem. Sci., 2018,9, 2270-2283
  • Open access: Creative Commons BY license
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    Direct observation of vibrational energy dispersal via methyl torsions

    Adrian M. Gardner, W. D. Tuttle, L. E. Whalley and T. G. Wright, Chem. Sci., 2018, 9, 2270
    DOI: 10.1039/C7SC05309F

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