The photodissociation dynamics of hexafluoropropene examined at 193 nm

The photodissociation of hexafluoropropene at 193 nm was studied using photofragment translational spectroscopy. One primary channel results in loss of a fluorine atom; from the maximum translational energy release, a value of 121 kcal/mol was determined to be the upper limit for the CF bond dissociation energy. In addition, elimination of CF2 and CF3 compeetes with C-F bond cleavage. A branching fraction, CF2:F:CF3, of 0.42:0.41:0.17 was found among these three primary channels. A comparison of UV photolysis and infrared multiphoton dissociation experiments suggests that excitation and dissociation on an excited state surface competes with internal conversion and dissociation from the ground state.