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Product state distributions of thermal energy ion-molecule reactions are determined by the sensitive optical methods of infrared chemiluminescence and laser-induced fluorescence detection. Experiments to obtain detailed vibrational state populations are carried out in a flowing afterglow ion source. Product state information is obtained for a series of proton transfer reactions and charge transfer reactions, which reveals many aspects of the dynamical behaviors of these processes. Measurements are also presented for polyatomic ion-molecule reactions, for optically-determined rates of ion collisional excitation and deactivation, and on visible chemiluminescence yields and branching fractions for reactions important in the aurora.