High resolution photoelectron spectra of the vinoxide anion are obtained by slow electron velocity-map imaging. Transitions between the anion X̃A1 ground electronic state and the radical X̃A2 and ÃA2 states are observed. This experiment yields a precise value of 1.8250±0.0012eV for the adiabatic electron affinity and 0.996±0.003eV for the Ã-X̃ term energy of the vinoxy radical. Franck–Condon simulations of the X̃A2X̃A1 transition are performed at varying levels of approximation. Full treatment with Duschinsky rotation is necessary to reproduce experimental results. Comparison of the experimental and simulated spectra leads to the assignment of previously unresolved transitions, notably between levels of a symmetry.

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