Direct observation of vibrational energy dispersal via methyl torsions.

Direct observation of vibrational energy dispersal via methyl torsions.
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DOI:
10.1039/c7sc05309f
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发表时间:
2018-02-28
期刊:
影响因子:
8.4
通讯作者:
Wright TG
Wright TG
中科院分区:
化学1区
文献类型:
--
作者:
Gardner AM;Tuttle WD;Whalley LE;Wright TG

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Explicit evidence for the role of methyl rotor levels in promoting energy dispersal is reported. 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.
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