Two of the 3p Rydberg transitions of the methylbenzenes are seen in their multiphoton ionization spectra. These are assigned to states which include the 3pz orbital, having symmetries 1A1 and 1B2 in toluene and 1B1u and 1B2u in p-xylene. The origins of these states appear at 52839 and 54734 cm−1 in toluene. The 3s Rydberg transitions do not appear strongly in these spectra, indicating that the 3pz states have a longer lifetime with respect to radiationless transitions or dissociation.
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