Rate coefficient measurements for the ClO radical self-reaction as a function of pressure and temperature

Halogen chemistry plays an important role in polar stratospheric ozone loss. The ClO dimer (Cl2O2) catalytic ozone destruction cycle accounts for the vast majority of winter/spring polar stratospheric ozone loss. A key step in the dimer catalytic cycle is the pressure and temperature dependent self-reaction of the ClO radical. The rate coefficient for the ClO self-reaction has been measured in previous laboratory studies but uncertainties persist, particularly at atmospherically relevant temperatures and pressures. In this laboratory study, rate coefficients for the ClO self-reaction were measured over a range of temperature (200 - 296 K) and pressure (50 - 600 Torr, He and N2 bath gases). ClO radicals were produced by pulsed laser photolysis of Cl2O at 248 nm. The ClO radical temporal profile was measured using dual wavelength cavity ring-down spectroscopy (CRDS) near 280 nm. The absolute ClO radical concentration was determined using the ClO UV absorption cross sections and their temperature dependence measured as part of this work. The results from this work will be compared with previous studies and the discrepancies discussed. Possible explanations for deviations of the reaction rate coefficient from the simple Falloff kinetic behavior currently recommended for use in atmospheric model calculations will be discussed.