Accurate Kinetic Studies of OH + HO2 Radical-Radical Reaction through Direct Measurement of Precursor and Radical Concentrations with High-Resolution Time-Resolved Dual-Comb Spectroscopy.

Abstract

The radical-radical reaction between OH and HO2 has been considered for a long time as an important reaction in tropospheric photochemistry and combustion chemistry. However, a significant discrepancy of an order of magnitude for rate coefficients of this reaction is found between two recent experiments. Herein, we investigate the reaction OH + HO2 via direct spectral quantification of both the precursor (H2O2) and free radicals (OH and HO2) upon the 248 nm photolysis of H2O2 using infrared two-color time-resolved dual-comb spectroscopy. With quantitative and kinetic analysis of concentration profiles of both OH and HO2 at varied conditions, the rate coefficient kOH+HO2 is determined to be (1.10 ± 0.12) × 10-10 cm3 molecule-1 s-1 at 296 K. Moreover, we explore the kinetics of this reaction under conditions in the presence of water, but no enhancement in the kOH+HO2 can be observed. This work as an independent experiment plays a crucial role in revisiting this prototypical radical-radical reaction.