Kinetics of the Reactions of Methyl Radical with Hydrogen, Methyl and Ethyl Peroxides

The HOOH+CH 3 , CH 3 OOH+CH 3 and CH 3 CH 2 OOH+CH 3 reactions were characterized using accurate ab initio methods with reliable basis sets. The reaction rate constants were calculated by canonical variational transition state theory as applied to a complex mechanism involving the formation of reactant complexes. The formation of aldehyde or formaldehyde was observed when the CH 3 radical attacks on the CH 2 group in CH 3 CH 2 OOH or on the CH 3 group in CH 3 OOH. The results showed that the channels of H‐abstraction from OH group are dominant channels at low temperature, while the channels of OH‐transfer to CH 3 become predominant with increasing temperature. For the CH 3 OOH+CH 3 reaction, the channel producing CH 2 O+OH and the OH‐transfer channel have a similar rate coefficient.