Molecular effusive beam and dispersed synchrotron radiation at SuperACO positron storage ring allowed an investigation of the complete outer‐ and inner‐valence shells photoionization of gaseous SnCl2 for the first time. New and resonating features in the inner‐valence region were observed in the photoelectron spectrum of this molecule. Auger processes following the relaxation of Sn 4d hole in the free molecule SnCl2 were detected, analogus to those observed in atomic tin.

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