Metastable states in NO2+ probed with Auger spectroscopy.

High-resolution N 1s and O 1s photoelectron spectra (PES) of NO are presented together with spectra of the subsequent Auger decay. The PES are analyzed by taking spin–orbit splitting of the 2Π ground state into account providing detailed information on equilibrium distances, vibrational energies, and lifetime widths of the core-ionized states. In the Auger electron spectra (AES) transitions to five metastable dicationic final states are observed, with two of them previously unobserved. A Franck–Condon analysis of the vibrational progressions belonging to these transitions provides detailed information on the potential-energy curves of the dicationic final states as well as on the relative Auger rates. The present calculations of the potential-energy curves of NO2+ agree well with the experimental results and allow an assignment of the two hitherto unresolved Auger transitions to excited states of NO2+, C2Σ+and c4Π.