Detailed course of the O + HO2 reaction

The elementary radical-radical reactions that are of such importance in laser, astrophysical, atmospheric, and combustion processes are increasingly open to direct rate measurement. Attention is presently given to the O + HO2 reaction, which has only one exothermic product channel: OH + O2. Isotopic product analysis was conducted spectroscopically using laser-induced fluorescence of OH. It is found that the simple atom-radical reaction takes place by way of the rapid formation and breakup of an unexpected radical intermediate, thereby raising questions as to the formation, thermochemistry, and decomposition of poorly known products in many other radical-radical reaction systems.