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

Abstract

The vibrationally structured 3p(z) 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) over 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 3p(y) and 3p(x) excitation thresholds, found to differ by only 10-30 meV, lie around 6.4 eV corresponding to the first intense (C) over 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.