Abstract
We measure threshold photoelectron spectra of the benzyl radical, which show transitions to at least three electronic states of the benzylium cation: 1A1, 3B2, and 1B2, with possible contributions from transitions to 3A1. The main features in the vibrationally resolved threshold photoelectron spectrum between 7.1 and 10.5 eV are assigned with the aid of Franck–Condon simulations to these four electronic states of benzylium. We measure the adiabatic ionisation energy of the benzyl radical to be 7.252(5) eV and observe a well-resolved vibrational progression in the lowest triplet state, 3B2, from which we obtain a measured singlet–triplet splitting of 1.928(7) eV in benzylium.
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