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We have studied fluorescence spectra of small Xem and Xem(NF3)k clusters (m,k⩽102) embedded in large host Ne7500 clusters, excited with SR excitation in the VUV spectral region above the Xe+(P1∕22) atomic limit. The IR emission bands due to ionic chromophores Xep+ (p=2,3,4) as well as UV (B–X) and visible (C–A) bands due to desorbed Xe+F− excimer molecules have been observed. The triatomic Xe2F excimer emission has only been observed under low-energy excitation close to the lowest xenon exciton absorption band. A competition between ionic and charge-transfer reaction channels is followed as a function of the cluster sizes m and k.

Ionic chromophores Xep+ (p⩽4) in multishell rare-gas clusters Xem(NF3)kNe7500 (m,k⩽100) studied with fluorescence spectroscopy