Abstract
The higher Rydberg states of jet-cooled C6H6, C6D6(n⩽30) and C6H5F(n⩽13) have been studied using two-photon resonance-enhanced multiphoton ionization (REMPI) spectroscopy. In C6H6 and C6D6 long series of three gerade nd Rydberg series converging on the first ionization potential, previously observed up to n=8, are extended up to n=30. The spectra are dominated by origin transitions with only weak vibrational structure being observed. The series with A1g and E1g or E2g symmetry were distinguished by polarization experiments. Similar long series of three nd Rydberg states are also observed for C6H5F and are reported here for the first time. In contrast to benzene, more vibrational activity, especially in ν6a was observed, and thus Rydberg series can only be resolved up to n=12 for C6H5F.
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