IR fluorescence studies of the IR multiple-photon dissociation of the system CDF₃-CHF₃

Abstract

Time-resolved IR emissions were obtained for IR multiple-photon excitation/dissociation of CDF₃ at 970 cm^-1 in neat form and its mixtures with CHF₃ and argon at moderate pressures. Enhancements in emission intensities were observed for CDF₃^∗ and DF^∗ on addition of argon. The bimodal exponential decay observed for both CDF₃^∗ and DF^∗ emissions in the neat photolysis of CDF₃ changed into single-mode decay when the sample was irradiated in the presence of argon at a focal fluence of 95 J cm^-2. The bimolecular rate constant for collisional deactivation of CDF₃^∗ by argon was 1.3 × 10³ s^-1 Torr^-1. In situ selectivity factors were determined from the measurements of DF^∗ and HF^∗ emission intensities in the photolysis of 1:1 CDF₃-CHF₃ mixtures.