The Rydberg 3p multiplet structure of the fenchone C band absorption

Powis, Ivan; Singh, Dhirendra P.

Abstract

The vibrationally structured 3pz Rydberg excitation is identified and assigned in the VUV absorption spectrum of fenchone with an origin at 6.31 eV, below the prominent 6.4 eV C̃ (nominally 3p) band onset. This feature cannot, however, be observed in (2+1) REMPI spectra, as its relative excitation cross-section is much reduced in a two-photon transition. The 3py and 3px excitation thresholds, found to differ by only 10-30 meV, lie around 6.4 eV corresponding to the first intense C̃ band peak in both VUV and REMPI spectra. Calculations of vertical and adiabatic Rydberg excitation energies, photon absorption cross-sections, and vibrational profiles are used to support these interpretations.

Citation

Powis, I., & Singh, D. P. (2023). The Rydberg 3p multiplet structure of the fenchone C band absorption. Physical Chemistry Chemical Physics, 25(25), 16712-16717. https://doi.org/10.1039/d3cp01572f

• Journal Article Type: Article
• Acceptance Date: May 31, 2023
• Online Publication Date: Jun 1, 2023
• Publication Date: Jul 7, 2023
• Deposit Date: Jul 3, 2023
• Publicly Available Date: Jul 4, 2023
• Journal: Physical Chemistry Chemical Physics
• Print ISSN: 1463-9076
• Electronic ISSN: 1463-9084
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 25
• Issue: 25
• Pages: 16712-16717
• DOI: https://doi.org/10.1039/d3cp01572f
• Keywords: Physical and Theoretical Chemistry; General Physics and Astronomy
• Public URL: https://nottingham-repository.worktribe.com/output/22435145
• Publisher URL: https://pubs.rsc.org/en/content/articlelanding/2023/CP/D3CP01572F