Torsion and vibration-torsion levels of the S1 and ground cation electronic states of para-fluorotoluene

Gardner, Adrian M.; Tuttle, William D.; Whalley, Laura; Clayton, Andrew; Carter, Joseph H.; Wright, Timothy G.

Abstract

We investigate the low-energy transitions (0–570 cm-1) of the S1 state of para-fluorotoluene (pFT) using a combination of resonance-enhanced multiphoton ionization (REMPI) and zero-kinetic-energy (ZEKE) spectroscopy and quantum chemical calculations. By using various S1 states as intermediate levels, we obtain zero-kinetic-energy (ZEKE) spectra. The differing activity observed allows detailed assignments to be made of both the cation and S1 low-energy levels. The assignments are in line with the recently-published work on toluene from the Lawrance group [J. Chem. Phys. 143, 044313 (2015)], which considered vibration-torsion coupling in depth for the S1 state of toluene. In addition, we investigate whether two bands that occur in the range 390–420 cm-1 are the result of a Fermi resonance; we present evidence for weak coupling between various vibrations and torsions that contribute to this region. This work has led to the identification of a number of misassignments in the literature, and these are corrected.

Citation

Gardner, A. M., Tuttle, W. D., Whalley, L., Clayton, A., Carter, J. H., & Wright, T. G. (in press). Torsion and vibration-torsion levels of the S1 and ground cation electronic states of para-fluorotoluene. Journal of Chemical Physics, 145(124307), https://doi.org/10.1063/1.4962822

• Journal Article Type: Article
• Acceptance Date: Sep 2, 2016
• Online Publication Date: Sep 26, 2016
• Deposit Date: Sep 5, 2016
• Publicly Available Date: Sep 26, 2016
• Journal: Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: American Institute of Physics
• Peer Reviewed: Peer Reviewed
• Volume: 145
• Issue: 124307
• DOI: https://doi.org/10.1063/1.4962822
• Public URL: https://nottingham-repository.worktribe.com/output/809320
• Publisher URL: http://scitation.aip.org/content/aip/journal/jcp/145/12/10.1063/1.4962822
• Contract Date: Sep 5, 2016