J. Leclaire, R. Anand, Philip J. M. Johnson
May 1, 1997
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Influential Citations
23
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Journal
Journal of Chemical Physics
Abstract
The newly developed technique of photoinduced Rydberg ionization (PIRI) spectroscopy has been successfully applied to study the B←X transition in the phenol and phenol-d6 cations. Vibrationally resolved spectra have been obtained for the B state in phenol ion via the origin and the ν6, and ν12 vibrations of the ground ionic state. Similarly, vibrationally resolved spectra for the B state in phenol-d6 ion have been obtained via the origin and ν6 vibration. Calculations to date have suggested the character of the half-filled orbital is π type, and experimental evidence for the B-state assignment so far has been inconclusive. In contrast to previous featureless photoelectron spectra, the main feature in all of the spectra presented here is the presence of several long, low frequency Frank–Condon progressions, suggestive of a large geometry change in the transition. Configuration interaction singles 6-31G* calculations, allowing full geometry optimization, show that the first excited σ state has the OH g...