C–C bond fission pathways of chloroalkenyl alkoxy radicals
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DFT and ab initio molecular orbital calculations of the chloroalkenyl alkoxy radicals from the Cl-initiated reaction of isoprene and their decomposition pathways were carried out. The geometries and energetics of the six isomers of the alkoxy radicals as well as the transition states and products of their decomposition reactions were investigated. Furthermore, the high-pressure limit rate constants of the C-C bond fission of the chloroalkenyl alkoxy radicals were calculated using the presently obtained activation energies and TST. The results indicate rather slow decomposition rates of the chloroalkenyl alkoxy radicals, consistent with laboratory studies, indicating small MVK and MACR yields but significant CMBO formation. A yield of 30% was predicted for CMBO formation from Cl-initiated oxidation of isoprene.
author list (cited authors)
Zhang, D., Zhang, R., & Allen, D. T.