IR multiphoton photochemistry of CF3Cl

CF3Cl has been dissociated using the focused output of a CO2 TEA laser operating on the R(40) line of the 9.6 μm band. IR fluorescence has been observed for HF and HCl after irradiating mixtures of CF3Cl, HBr, and Ar, indicating the production of F as well as Cl. In addition, the laser-induced fluorescence spectrum of CF2 has been observed using a KrF laser (249 nm) to excite the CF2 Ã1B1←X̃1A1 transition. A two step dissociation mechanism in which CF3 and Cl are the primary products followed by the subsequent multiphoton absorption and dissociation of CF3 to produce CF2 and F is proposed. Evidence for secondary dissociation of CF3 has been demonstrated by observing CF2 in the infrared multiphoton dissociation of C2F6, which is known to produce CF3 at low fluence. Further evidence in support of a two-step dissociation mechanism is given by analysis of stable products, fluence studies, and RRKM calculations.