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An energy resolved electron–ion coincidence study near the S 2p thresholds of the SF6 molecule

The fragmentation dynamics of the SF6 molecule following the excitations of S 2p electrons into unoccupied molecular orbitals has been studied using the energy-resolved electron–ion coincidence technique. Fragmentation patterns were found to depend on the particular excitation and on the electronic state of the molecular ion. The spectator resonant Auger decay at the 2p → 6a1g resonance induces changes in the ion distributions as compared to direct photoionization. Furthermore, coincidence spectra related to the same Auger structure display different ion abundances at the 2t2g and 4eg shape resonances. Differences were also found in the Auger decay spectra. These findings give further support for the previously suggested many-electron character of the 4eg shape resonance.