期刊
CHEMICAL SCIENCE
卷 9, 期 8, 页码 2270-2283出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c7sc05309f
关键词
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资金
- EPSRC [EP/L021366/1]
- EPSRC
- University of Nottingham
- Engineering and Physical Sciences Research Council [EP/L021366/1] Funding Source: researchfish
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 zerokinetic-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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