Mixtures of halogen-containing molecules and rare gases have been excited by a short pulse of high energy electrons. The D′→A′ transitions occurring between an ionically bound upper level and a weakly bound covalent lower level in the diatomic halogens F2, Cl2, and interhalogen compounds ClF, ICl, IF, IBr, BrCl, and BrF formed under these conditions have been studied systematically. Emission wavelengths calculated from a simple model are in good agreement with the experimental data. The processes responsible for the population of the upper level have also been studied. The exchange reaction of an electronically excited atom with a halogen donor molecule appears to be the key step in the kinetic excitation sequence. A rate equation model satisfactorily describes the time development of the observed halogen fluorescence. Based on these results, successful laser experiments have been conducted on several of the interhalogen systems.

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