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
I-Yun Chen, Che-Wei Chang, Christa Fittschen, and Pei-Ling Luo*
J. Phys. Chem. Lett.,15, 3733–3739 (2024)
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.