Strong Selectivity in Symmetry forbidden vibronic transitions in Deep Core Ionic Photofragmentation of the SF6 molecule

•Photoionization of SF6 have been studied with X-ray photons around the S K edge.•The 1a1g → 6a1g transition plays a relevant role in the fragmentation pattern.•The F+ ion is the most abundant species observed in the energy range studied.•The intensity the dipole-forbidden (1a1g → 6a1g) was calculated.

Deep core photoionization of the sulfur hexafluoride molecule have been studied with X-ray photons at energies around the S K edge (from 2472 eV to 2489 eV), using time-of-flight multicoincidence technique with synchrotron radiation. Total and partial photoion yields for the fragments have been recorded as a function of the incident photon energy. The atomic fluorine ion, F+ is the most abundant species observed in the mass spectra at the energy range studied. The SF6 molecule undergoes a complete break up with the formation of atomic doubly and triply charged S2+, S3+, and F2+ fragments. The intensity of absorption for the dipole-forbidden but vibronically allowed transition S K (1a1g → 6a1g) was calculated and it is shown that it play a relevant role in the fragmentation pattern.

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