Abstract
Vibrational spectra of C6H6+ and C6D6+ in the first excited electronic state, B̃ 2E2g, have been measured by one-photon mass-analyzed threshold ionization spectroscopy using coherent vacuum ultraviolet radiation generated by four-wave sum frequency mixing in Hg. Ionization energies to C6H6+ and C6D6+ in the B̃ 2E2g state have been determined to be 11.4897±0.0006 and 11.5235±0.0006 eV, respectively. Vibrational spectra were much simpler than and different from those of the same state recorded by the gerade photo-induced Rydberg ionization technique reported previously. For some vibrations not much affected by the Jahn–Teller effect, assignments were possible by comparing with the calculated results. Assignments for the Jahn–Teller components were not definite, or rather arbitrary, even though decent fits were possible through multimode Jahn–Teller calculations.
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