Complete basis set ab initio computational study of unimolecular decomposition of dimethyl ether

Complete basis set ab initio computational study was performed with the target of elucidating decomposition paths in dimethyl ether combustion. Several parallel chemical transformations were considered with the determination of activation barriers, bond dissociation energies, and enthalpies of the reactions. It was determined that the formation of some carbene intermediates is an energetically unfavorable process, and that the reaction is occurring through C–O bond fusion, hydrogen radical abstraction, and elimination reaction. The computed values and reaction outcomes were compared to experimental results and the reliability of this computational approach for the study of combustion chemistry was discussed.