Publications

Theoretical kinetics of O + C2H4

Li, Xiaohu; Jasper, Ahren W.; Zador, Judit Z.; Miller, James A.; Klippenstein, Stephen J.

The reaction of atomic oxygen with ethylene is a fundamental oxidation step in combustion and is prototypical of reactions in which oxygen adds to double bonds. For 3O+C2H4 and for this class of reactions decomposition of the initial adduct via spin-allowed reaction channels on the triplet surface competes with intersystem crossing (ISC) and a set of spin-forbidden reaction channels on the ground-state singlet surface. The kinetics of 3O+C2H4 was studied using an ab initio transition state theory based master equation approach that includes an a priori description of ISC. The theoretical results were remarkably in good agreement with existing low-temperature experimental kinetics and molecular beam studies. Above approximately equal 1000 K CH2CHO+H and CH2+CH2O were predicted as the major products which differs from the room temperature preference for CH3+HCO and from the prediction of a previous detailed master equation study.