Electron stimulated desorption of negative and positive fluorine ions from BaF2 surfaces has been studied as a function of impact electron energy. Thresholds observed for F+ and F are correlated with core‐level binding energies of Ba atoms. We propose that core level ionization of Ba ions, followed by an interatomic Auger decay involving halogen ions, can initiate F+ desorption, while the formation and subsequent breakup of superexcited molecular complexes containing a core hole can lead directly to the ejection of negative ions.

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