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dc.contributor.authorMozurkewich, M.
dc.contributor.authorBenson, S.W.
dc.identifier.citationInt. J. Chem. Kin., 17, 787-807.en
dc.description.abstractThe negative temperature dependence, pressure dependence, and isotope effects of the self-reaction of HO2 are modeled, using RRKM theory, by assuming that the reaction proceeds via a cyclic, hydrogen-bonded intermediate. The negative temperature dependence is due to a tight transition state, with a negative threshold energy relative to reactants, for decomposition of the intermediate to products. A symmetric structure for this transition state reproduces the observed isotope effect. The weak pressure dependence for DO2 self-reaction is due to the approach to the high-pressure limit. Addition of a polar collision partner, such as ammonia or water vapor, enhances the rate by forming an adduct that reacts to produce deexcited intermediate. A detailed model is presented to fit the data for these effects. Large ammonia concentrations should make it possible to reach the high-pressure limit of the self-reaction of HO2.en
dc.rightsThe definitive version is available at www3.interscience.wiley.comen
dc.titleSelf-reaction of HO2 and DO2: negative temperature dependence and pressure effectsen

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