Theoretical study on the methyl radical with chlorinated methyl radicals CH(3-n)Cln (n = 1, 2, 3) and CCl2.
Radical-radical reactions involving chlorinated methyl radicals are particularly important in the mechanism of combustion of chlorinated hydrocarbons. Yet, they are usually difficult to study experimentally. In this paper, four chloride-related radical-radical reactions, i.e., CH3+CH(3-n)Cln (n = 1, 2, 3) and CH3+CCl2, are theoretically studied for the first time by means of the Gaussian-3//B3LYP potential energy surface survey combined with the master equation study over a wide range of temperatures and pressures. Our calculated results show that the three CH3+CH(3-n)Cln reactions can barrierlessly generate the former two kinetically allowed products P1 H(2)C=C(H)(3-n)Cl(n-1)+HCl and P2 CH3CH(3-n)Cl(n-1)+Cl with the very high predominance of P1 over P2. For the CH3 reaction with the biradical CCl2, which inevitably takes place during the CH3+CCl3 reaction and yet has never been studied experimentally or theoretically, H(2)C=CCl2+H and H(2)C=C(H)Cl+Cl are predicted to be the respective major and minor products. The results are compared with the recent laser photolysis/photoionization mass spectroscopy study on the CH3+CH(3-n)Cln (n = 1, 2, 3) reactions. The predicted rate constants and product branching ratios of the CH3+CCl2 reaction await future experimental verification.
Wang
Jian
J
State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People's Republic of China.
Ding
Yi-Hong
YH
Zhang
Shao-Wen
SW
Sun
Chia-Chung
CC