Application of an atomic relaxation model for the interpretation of O1s to Rydberg excited Auger electron spectra of molecular oxygen

Resonant and normal Auger electron spectra associated with an O1s initial vacancy of the O2 molecule have been recorded using photon energies of 541.80, 541.97 and 650 eV. The resonant Auger spectra obtained at 541.80 and 541.97 eV are interpreted as composed essentially of two characteristic parts, one between 10 and 35 eV binding energy reminiscent to direct photoionisation, and another, above 35 eV, associated primarily with spectator decay of the intermediate core-hole state. The spectra above 35 eV owe some similarity to the ordinary Auger electron spectrum recorded at 650 eV, and an interpretation is made in terms of Rydberg series in the cation converging towards the dicationic ionisation limits. The interpretation is based on a relaxation model introduced earlier for atomic resonant Auger spectra. The assignments of the resonant spectra assume that the relevant intermediate neutral states at 541.80 and 541.97 eV governing the Auger decay are essentially the ν = 0 and 1 vibrational components of the (O1s)−1 ( 4 Σ u - ) 4pσ Rydberg state. Arguments for this interpretation are given.