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Chemiluminescence from the electronic excited states of the cesium atom in the cesium–fluorine reaction system

The chemiluminescence of the cesium–fluorine reaction system has been analyzed spectroscopically to give steady‐state populations of the excited electronic states of the cesium atom. By correcting for cascade of excitation the primitive populations have been calculated, and these indicate a statistical distribution of electronic excitation. A phase space calculation of the distribution of electronic excitation agrees satisfactorily with experiment. Quantum yield measurements and nitrogen‐gas quenching experiments have also been performed to elucidate the reaction mechanics. It appears that the pumping mechanism involves the reaction of Cs with F2 to create vibrationally excited CsF, which then transfers its energy to Cs in a V–E process.