Internal state distribution of the CF fragment from the 193 nm photodissociation of CFCl and CFBr

The dynamics of the 193 nm photodissociation of the CFCl and CFBr molecules have been investigated in a molecular beam experiment. The CFCl and CFBr parent molecules were generated by pyrolysis of CHFCl2 and CFBr3, respectively, and the CFCl and the CF photofragment were detected by laser fluorescence excitation. The 193 nm attenuation cross section of CFCl was determined from the reduction of the CF photofragment signal as a function of the photolysis laser fluence. The internal state distribution was derived from the analysis of laser fluorescence excitation spectra in the A 2Sigma+-X 2Pi band system. A very low degree of rotational excitation, with essentially equal A' and A" Lambda-doublet populations, and no vibrational excitation were found in the CF photofragment. The energy available to the photofragments is hence predominantly released as translational energy. The CF internal state distribution is consistent with the dissociation of a linear intermediate state. Considerations of CFCl electronic states suggest that a bent Rydberg state is initially excited.