David J. Kemp
Unravelling overlaps and torsion-facilitated coupling using two-dimensional laser-induced fluorescence
Kemp, David J.; Gardner, Adrian M.; Tuttle, William D.; Wright, Timothy G.
Authors
Adrian M. Gardner
William D. Tuttle
Timothy G. Wright
Abstract
Two-dimensional laser-induced fluorescence (2D-LIF) spectroscopy is employed to identify contributions to fluorescence excitation spectra that arise from both overlapping bands and coupling between zero-order states (ZOSs). Evidence is found for the role of torsional motion in facilitating the coupling between vibrations that particularly involves the lowest-wavenumber out-of-plane vibrational modes. The experiments are carried out on jet-cooled p-fluorotoluene, where the molecules are initially in the lowest two torsional levels. Here we concentrate on the 390–420 cm−1 features in the S1 ← S0 excitation spectrum, assigning the features seen in the 2D-LIF spectrum, aided by separate dispersed fluorescence spectra. The 2D-LIF spectra allow the overlapping contributions to be cleanly separated, including some that arise from vibrational-torsional coupling. Various coupling routes open up because of the different symmetries of the lowest two torsional modes; these combine with the vibrational symmetry to provide new symmetry-allowed vibration-torsion (‘vibtor’) interactions, and the role of the excited m = 1 torsional level is found to be significant.
Citation
Kemp, D. J., Gardner, A. M., Tuttle, W. D., & Wright, T. G. (2019). Unravelling overlaps and torsion-facilitated coupling using two-dimensional laser-induced fluorescence. Molecular Physics, 117(21), 3011-3026. https://doi.org/10.1080/00268976.2018.1554865
| Journal Article Type | Article |
|---|---|
| Acceptance Date | Nov 27, 2018 |
| Online Publication Date | Dec 9, 2018 |
| Publication Date | Nov 2, 2019 |
| Deposit Date | Dec 10, 2018 |
| Publicly Available Date | Dec 10, 2019 |
| Journal | Molecular Physics |
| Print ISSN | 0026-8976 |
| Electronic ISSN | 1362-3028 |
| Publisher | Taylor & Francis Open |
| Peer Reviewed | Peer Reviewed |
| Volume | 117 |
| Issue | 21 |
| Pages | 3011-3026 |
| DOI | https://doi.org/10.1080/00268976.2018.1554865 |
| Keywords | Physical and Theoretical Chemistry; Biophysics; Molecular Biology; Condensed Matter Physics |
| Public URL | https://nottingham-repository.worktribe.com/output/1395124 |
| Publisher URL | https://www.tandfonline.com/doi/full/10.1080/00268976.2018.1554865 |
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