We examine the middle atmospheric odd-hydrogen (HO_x) chemistry by comparing the Aura Microwave Limb Sounder (MLS) OH and HO_2 measurements with a photochemical model simulation. The model underestimates mesospheric OH and HO_2 concentrations if the standard chemical kinetic rates are used, whether the model H_2O and O_3 are constrained with observations or not. To resolve the discrepancies, we adjust the kinetic rate coefficients of three key reactions (O + OH → O_2 + H, OH + HO_2 → H_2O + O_2, and H + O_2 + M → HO_2 + M) and the O2photo absorption cross section at Lyman-α (121.57 nm) using the Bayesian optimal estimation. A much better model-observation agreement can be achieved if the kinetic rate coefficients for H + O_2 + M → HO_2 + M is increased by 134–310%, and the O_2 photo absorption cross section at Lyman-α is reduced by 33–54%, while the kinetic rate coefficients for O + OH → O_2 + H and OH + HO_2 → H_2O + O_2 remain consistent with the current laboratory values. The kinetic rate coefficient for H + O_2 + M → HO_2 + M requires a very large adjustment beyond the uncertainty limits recommended in the NASA Data Evaluation, suggesting the need for future laboratory measurements. An alternative explanation is that the radiative association reaction, H + O_2 → HO_2 + hν, plays a significant role, which has never been measured. Our results demonstrate that high quality satellite observations can be used to constrain photochemical parameters and help improve our understanding of atmospheric chemistry
