Vibrational spectra of C6H6+ and C6D6+ in the ground electronic state have been measured by one-photon mass-analyzed threshold ionization (MATI) spectroscopy using coherent vacuum ultraviolet radiation generated by four wave mixing in Kr gas. The ionization energies of C6H6 and C6D6 determined by one-photon MATI, 74551±5 and 74579±5 cm−1, respectively, are similar to those reported previously. Vibrational spectra are much simpler than the previous zero kinetic energy photoelectron and MATI spectra obtained by two-photon excitation. Almost complete vibrational assignments for the cations have been possible, which will be useful for future theoretical studies of the Jahn-Teller effect in these cations. Implication from the present one-photon spectra agrees with the previous suggestion that the geometry of benzene cation in the ground electronic state belongs to the D6h symmetry.

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