Kinetic and mechanistic study of the reaction of O(1D) with CF2HBr

A laser flash photolysis–resonance fluorescence technique has been employed to investigate the kinetics and mechanism of the reaction of electronically excited oxygen atoms, O(1D), with CF2HBr. Absolute rate coefficients (k1) for the deactivation of O(1D) by CF2HBr have been measured as a function of temperature over the range 211–425 K. The results are well described by the Arrhenius expression k1(T) = 1.72 × 10−10 exp(+72/T) cm3molecule−1 s−1; the accuracy of each reported rate coefficient is estimated to be ±15% (2σ). The branching ratio for nonreactive quenching of O(1D) to the ground state, O(3P), is found to be 0.39 ± 0.06 independent of temperature, while the branching ratio for production of hydrogen atoms at 298 K is found to be 0.02−0.02+0.01. The above results are considered in conjunction with other published information to examine reactivity trends in O(1D) + CF2XY reactions (X,Y = H, F, Cl, Br).