Disentangling Auger decays in O₂ by photoelectron-ion coincidences

In non-resonant Auger electron spectroscopies, multi core-ionized states lead to numerous energetically close-lying electronic transitions in Auger spectra, this hampering the assignment and interpretation of the experimental results. Here we reveal a new method to overcome this intrinsic limitation of non-resonant inner-shell spectroscopies. In a proof-of-principle experiment performed for the O₂ molecule, most of the Auger final states are dissociative, and we measure in coincidence the kinetic energy of the photoelectron and the kinetic energy release of the (O⁺, O⁺) ion pairs produced after the Auger decay of the O 1s^-1 core-ionized states. The Auger final states are assigned using energy conservation. We fully separate the contributions from the ⁴Σ^- and ²Σ^- intermediate ionic states and conclusively demonstrate that the Auger decay probability can dramatically depend on the different O₂ 1s ^-1 intermediate multiplet states. In addition, a metastable Auger final state also exists, with lifetime longer than 3.8 μs, and clear changes are observed in both branching ratio and spectral profile of the O 1s photoelectron spectrum when they are recorded in coincidence with either [Formula: see text] or with other ionic species. These changes are attributed to the population of the metastable [Formula: see text] Auger final state via different intermediate states.