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Updated: Jul 26, 2025

Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F−
Published on: July 27, 2018
The Rydberg 3p multiplet structure of the fenchone C band absorption
Ivan Powis1, Dhirendra P Singh1
1School of Chemistry, The University of Nottingham, University Park, Nottingham NG7 2RD, UK. ivan.powis@nottingham.ac.uk.
Abstract:
The vibrationally structured 3p 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 3p and 3p 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.
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