Issue 25, 2023

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

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 [C with combining tilde] (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 [C with combining tilde] 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.

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

Article information

Article type
Communication
Submitted
06 Apr 2023
Accepted
31 May 2023
First published
01 Jun 2023
This article is Open Access
Creative Commons BY-NC license

Phys. Chem. Chem. Phys., 2023,25, 16712-16717

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

I. Powis and D. P. Singh, Phys. Chem. Chem. Phys., 2023, 25, 16712 DOI: 10.1039/D3CP01572F

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