Identification of separate isoenergetic routes for vibrational energy flow in p-fluorotoluene

Gardner, Adrian M.; Whalley, Laura E.; Kemp, David J.; Tuttle, William D.; Wright, Timothy G.

Abstract

A deceptively simple feature in the S1 ← S0 spectrum of p-fluorotoluene (pFT), 1013 cm−1 above the origin, is studied using both zero-electron-kinetic-energy (ZEKE) and two-dimensional laser-induced fluorescence (2D-LIF) spectroscopy. It is found to consist of a cornucopia of overlapped transitions to eigenstates that arise from numerous interacting levels. A significant variation in the activity is seen employing both the ZEKE and 2D-LIF techniques. Detailed insight into the complicated spectra can be achieved, owing to the large number of vibrational wavenumbers that have been previously determined for the S0, S1, and D0+ states, summarized herein. It is found that the activity is dominated by two overtones, which are individually interacting with other levels, so providing largely independent routes for vibrational energy flow at the same internal energy. Additionally, other weak features located 900–1050 cm−1 above the origin are examined.

Citation

Gardner, A. M., Whalley, L. E., Kemp, D. J., Tuttle, W. D., & Wright, T. G. (2019). Identification of separate isoenergetic routes for vibrational energy flow in p-fluorotoluene. Journal of Chemical Physics, 151(15), https://doi.org/10.1063/1.5126179

• Journal Article Type: Article
• Acceptance Date: Sep 26, 2019
• Online Publication Date: Oct 15, 2019
• Publication Date: Oct 21, 2019
• Deposit Date: Oct 25, 2019
• Publicly Available Date: Oct 25, 2019
• Journal: Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: AIP Publishing
• Peer Reviewed: Peer Reviewed
• Volume: 151
• Issue: 15
• Article Number: 154302
• DOI: https://doi.org/10.1063/1.5126179
• Public URL: https://nottingham-repository.worktribe.com/output/2964774
• Publisher URL: https://aip.scitation.org/doi/10.1063/1.5126179
• Additional Information: This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Identification of separate isoenergetic routes for vibrational energy flow in p-fluorotoluene Adrian M. Gardnera), Laura E. Whalley, David J. Kemp, William D. Tuttle, and Timothy G. Wright) View AffiliationsThe Journal of Chemical Physics 151:15 and may be found at https://aip.scitation.org/doi/10.1063/1.5126179