Bimolecular reaction of molecular oxygen with overtone excited HOOH: Implications for recycling HO2 in the atmosphere
Abstract
We report ab initio calculations of important regions of the potential energy surface for the reaction: O2(3Σ−g) + HOOH → 2 HO2. The reaction is endothermic by 37.5 ± 3 kcal mol−1, as calculated at the QCISD(T)/6-311++G(3df,3pd)//QCISD/6-311G(2df,2p) level of theory. The predicted mechanism is via a simple hydrogen abstraction, with a barrier of 35.3 kcal mol−1, followed by formation of a six-membered complex, which breaks up into two HO2 radicals. If an OH stretching type local vibrational mode of the