Photodissociation dynamics of perfluorinated anhydrides: CO2 product bending excitation

Perfluorinated acetic anhydride (PFAA), succinic anhydride (PFSA), and glutaric anhydride (PFGA), were photolyzed at 222 nm. Time-resolved infrared diode laser absorption spectroscopy was used to monitor the CO2 photoproduct. The CO2 0nn0 bending state populations were characterized by vibrational Boltzmann temperatures of 1120±60, 2100±200, and 3100±1000 K for PFAA, PFGA, and PFSA, respectively. The general trend in 0nn0 excitation was consistent with the variation in total available energy. Small differences in relative 0001 population, compared with the bending states, were also observed, possibly indicating the presence of dynamical effects.