Complexity surrounding an apparently simple Fermi resonance in p-fluorotoluene revealed using two-dimensional laser-induced fluorescence (2D-LIF) spectroscopy

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

Abstract

Two-dimensional laser-induced fluorescence (2D-LIF) spectroscopy is a powerful tool allowing overlapped features in an electronic spectrum to be separated, and interactions between vibrations and torsions to be identified. Here the technique is employed to assign the 790–825 cm−1 region above the origin of the S1 ← S0 transition in para-fluorotoluene, which provides insight into the unusual time-resolved results of Davies and Reid [Phys. Rev. Lett. 109, 193004 (2012)]. The region is dominated by a pair of bands that arise from a Fermi resonance; however, the assignment is complicated by contributions from a number of overtones and combinations, including vibration-torsion (“vibtor”) levels. The activity in the 2D-LIF spectra is compared to the recently reported zero-electron-kinetic-energy spectra [Tuttle et al., J. Chem. Phys. 146, 244310 (2017)] to arrive at a consistent picture of the energy levels in this region of the spectrum.

Citation

Kemp, D. J., Whalley, L. E., Gardner, A. M., Tuttle, W. D., Warner, L. G., & Wright, T. G. (2019). Complexity surrounding an apparently simple Fermi resonance in p-fluorotoluene revealed using two-dimensional laser-induced fluorescence (2D-LIF) spectroscopy. Journal of Chemical Physics, 150(6), 064306/1-064306/14. https://doi.org/10.1063/1.5083682

• Journal Article Type: Article
• Acceptance Date: Jan 19, 2019
• Online Publication Date: Feb 11, 2019
• Publication Date: Feb 14, 2019
• Deposit Date: Mar 4, 2019
• Publicly Available Date: Mar 4, 2019
• Journal: The Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: American Institute of Physics
• Peer Reviewed: Peer Reviewed
• Volume: 150
• Issue: 6
• Article Number: 064306
• Pages: 064306/1-064306/14
• DOI: https://doi.org/10.1063/1.5083682
• Keywords: Physical and Theoretical Chemistry; General Physics and Astronomy
• Public URL: https://nottingham-repository.worktribe.com/output/1602385
• 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 Complexity surrounding an apparently simple Fermi resonance in p-fluorotoluene revealed using two-dimensional laser-induced fluorescence (2D-LIF) spectroscopy, David J. Kemp, Laura E. Whalley, Adrian M. Gardner, William D. Tuttle, Lewis G. Warner, and Timothy G. Wright, The Journal of Chemical Physics 2019 150:6 and may be found at https://doi.org/10.1063/1.5083682