Identifying complex Fermi resonances in p-difluorobenzene using zero-electron-kinetic-energy (ZEKE) spectroscopy

Kemp, David J.; Gardner, Adrian M.; Tuttle, William D.; Midgley, Jonathan; Reid, Katharine L.; Wright, Timothy G.

Abstract

The vibrations of the ground state cation (X ̃2B2g) of para-difluorobenzene (pDFB) have been investigated using zero-electron-kinetic-energy (ZEKE) spectroscopy. A comprehensive set of ZEKE spectra were recorded via different vibrational levels of the S1 state (< 00 + 1300 cm 1). The adiabatic ionization energy (AIE) for pDFB was measured as 73869±5 cm 1. Use of different intermediate levels allows different cationic vibrational activity to be obtained via the modification of the Franck-Condon factors for the ionization step, allowing the wavenumbers of different vibrational levels in the cation to be established. In addition, assignment of the vibrational structure in the ZEKE spectra allowed interrogation of the assignments of the S1  S0 transition put forward by Knight and Kable [A. E. W. Knight and S. H. Kable, J. Chem. Phys. 89, 7139 (1988)]. Assignment of the vibrational structure has been aided by quantum chemical calculations. In this way it was possible to assign seventeen of the thirty vibrational modes of the ground state pDFB+ cation. Evidence for complex Fermi resonances in the S1 state, i.e. those that involve more than two vibrations, was established. One of these was investigated using picosecond time-resolved photoelectron spectroscopy. In addition, we discuss the appearance of several symmetry-forbidden bands in the ZEKE spectra, attributing their appearance to a Rydberg state variation of an intrachannel vibronic coupling mechanism.

Citation

Kemp, D. J., Gardner, A. M., Tuttle, W. D., Midgley, J., Reid, K. L., & Wright, T. G. (2018). Identifying complex Fermi resonances in p-difluorobenzene using zero-electron-kinetic-energy (ZEKE) spectroscopy. Journal of Chemical Physics, 149(9), 094301. https://doi.org/10.1063/1.5045544

• Journal Article Type: Article
• Acceptance Date: Aug 16, 2018
• Online Publication Date: Sep 5, 2018
• Publication Date: Sep 7, 2018
• Deposit Date: Sep 6, 2018
• Publicly Available Date: Sep 6, 2018
• Journal: The Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: American Institute of Physics
• Peer Reviewed: Peer Reviewed
• Volume: 149
• Issue: 9
• Pages: 094301
• DOI: https://doi.org/10.1063/1.5045544
• Keywords: Physical and Theoretical Chemistry; General Physics and Astronomy
• Public URL: https://nottingham-repository.worktribe.com/output/1062414
• Publisher URL: https://aip.scitation.org/doi/10.1063/1.5045544
• Contract Date: Sep 6, 2018