Lifetime-vibrational interference in the autoionization of core-excited O2

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Abstract
The electron–electron coincidence technique has been used to measure the spectrum of autoionizing (Auger) electrons that are emitted following excitation of a core (1s) electron in O2 to the half‐filled 1πg orbital. The highest kinetic energy peak in the deexcitation spectrum corresponds to a transition to the ground state of O+2(X,2Πg). The energy, width, and shape of the observed peak cannot be described by pure Franck–Condon vibrational calculations. Because the lifetime for deexcitation is comparable to a vibrational period, interference between vibrational levels in the core‐excited state must be taken into account in calculating the transition profile. When this is done the agreement between observed and calculated line shapes is excellent.