Direct observation of vibrational energy dispersal via methyl torsions
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-dimension...
| Main Authors: | , , , |
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| Format: | Article |
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Royal Society of Chemistry
2018
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| Online Access: | https://eprints.nottingham.ac.uk/49331/ |
| _version_ | 1848797974913613824 |
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| author | Gardner, Adrian M. Tuttle, William D. Whalley, Laura E. Wright, Timothy G. |
| author_facet | Gardner, Adrian M. Tuttle, William D. Whalley, Laura E. Wright, Timothy G. |
| author_sort | Gardner, Adrian M. |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | 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. |
| first_indexed | 2025-11-14T20:12:24Z |
| format | Article |
| id | nottingham-49331 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T20:12:24Z |
| publishDate | 2018 |
| publisher | Royal Society of Chemistry |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-493312020-05-04T19:28:12Z https://eprints.nottingham.ac.uk/49331/ Direct observation of vibrational energy dispersal via methyl torsions Gardner, Adrian M. Tuttle, William D. Whalley, Laura E. Wright, Timothy G. 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. Royal Society of Chemistry 2018-01-24 Article PeerReviewed 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 http://pubs.rsc.org/en/Content/ArticleLanding/2018/SC/C7SC05309F#!divAbstract doi:10.1039/C7SC05309F doi:10.1039/C7SC05309F |
| spellingShingle | Gardner, Adrian M. Tuttle, William D. Whalley, Laura E. Wright, Timothy G. Direct observation of vibrational energy dispersal via methyl torsions |
| title | Direct observation of vibrational energy dispersal via methyl torsions |
| title_full | Direct observation of vibrational energy dispersal via methyl torsions |
| title_fullStr | Direct observation of vibrational energy dispersal via methyl torsions |
| title_full_unstemmed | Direct observation of vibrational energy dispersal via methyl torsions |
| title_short | Direct observation of vibrational energy dispersal via methyl torsions |
| title_sort | direct observation of vibrational energy dispersal via methyl torsions |
| url | https://eprints.nottingham.ac.uk/49331/ https://eprints.nottingham.ac.uk/49331/ https://eprints.nottingham.ac.uk/49331/ |