Abstract
Vibrationally resolved partial photoionization cross sections of O2 leading to the b4Σ−g and B2Σ−1g(3σ−1g) tonic states have been measured at high resolution in a wide photon energy range from 0.5 eV above threshold to 24.5 eV. The σu shape resonance is observed around 21.5 eV, in fairly good agreement with “one-electron” theoretical predictions. The series of resonances from 19 to 20 5 eV result from an autoionization process with a strong vibrational selectivity, explained by the similar geometries of the resonance states and the b ionic state. The large resonance widths originate from a strong Rydberg-valence orbital mixing Calculations using multichannel quantum defect theory reproduce the most important features.
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