We have measured threshold photoionization spectra of benzyl+h7, benzyl+‐αd2, and benzyl+d7 in the ground electronic state (X̃+1A1) using resonant two‐photon excitation and detection of electrons by pulsed field ionization. The adiabatic ionization potentials of benzyl‐h7, benzyl‐αd2, and benzyl‐d7 are 58 468±5 cm−1, 58 418±5 cm−1, and 58 386±5 cm−1. Excitation through a variety of vibronically mixed Ã 2A2B̃ 2B2 neutral excited states allows observation of cation vibrations of both a1 and b1 symmetries. We directly measure in‐plane fundamentals and infer the frequencies of certain out‐of‐plane fundamentals from their involvement in combinations or overtones. By comparison with harmonic frequencies from abinitio calculations, we assign 35 of 48 observed levels in the ‐h7 isotopomer, 15 of 22 levels in ‐αd2, and 25 of 30 levels in ‐d7. Abinitio calculations permit a detailed comparison of the geometry, chemical bonding, and vibrational frequencies in the benzyl anion, neutral, and cation. The anion and cation, both closed‐shell species, have remarkably similar geometries with relatively short exocyclic CC bond (1.371 Å and 1.372 Å, respectively) and with the aromatic ring compressed along the C2 symmetry axis. The neutral free radical has a longer exocyclic CC bond (1.413 Å) and a more nearly sixfold symmetric ring. The natural resonance theory provides bond orders and resonance‐structure weights in all three species. While no single resonance structure dominates in any of the three species, the structure with an exocyclic CC double bond is significantly more important in the anion and cation than in the neutral.

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