Laser photodissociation of fluorinated molecular dications Original Research Article

The results of experiments are reported to identify the ionic photoproducts produced by the interaction of gaseous dications, CF32+, SF42+, SF32+, SF22+, and SF2+, with tunable pulsed laser radiation in the visible and at the fixed wavelenghts of 355, 532, and 1064 nm. The experiments show that CF32+, SF32+, SF22+ and SF2+ readily absorb visible light and are promoted to excited states which dissociate by both neutral-loss and charge separation. Detailed studies of CF32+ show that the dissociation occurs by single-photon absorption which promotes the molecule to unbound excited states. Excitation thresholds for the photoinduced neutral-loss and charge separation reactions of SF2+ and SF32+ are apparent from the data. A qualitative interpretation of the competition between the neutral loss and charge separation processes is discussed in terms of a simple model of the potential energy surfaces.