Disentangling Auger decays in O(2) 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 O(2) 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 (4)Σ(−) and (2)Σ(−) intermediate ionic states and conclusively demonstrate that the Auger decay probability can dramatically depend on the different O(2) 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.