Gaseous reaction mechanism of C2F radical with water.
The kinetic properties of the carbon-fluorine radicals are little understood except those of CFn (n =1-3). In this article, a detailed mechanistic study was reported on the gas-phase reaction between the simplest pi-bonded C2F radical and water as the first attempt to understand the chemical reactivity of the C2F radical. Various reaction channels are considered. The most kinetically competitive channel is the quasi-direct hydrogen-abstraction route forming P5 HCCF + OH. At the CCSD(T)/6-311+G(2d,2p)//B3LYP/6-311G(d,p)+ZPVE, CCSD(T)/6-311+G(3df,2p)//QCISD/6-311G(d,p)+ZPVE and Gaussian-3//B3LYP/6-31G(d) levels, the overall H-abstraction barriers (4.5, 4.7, and 4.2 kcal/mol) for the C2F + H2O reaction are comparable to the corresponding values (5.5, 3.7, and 5.7 kcal/mol) for the analogous C2H + H2O reaction. This suggests that C2F is a reactive radical like the extensively studied C2H, in contrast to the situation of the CF and CF2 radicals that have much lower reactivity than the corresponding hydrocarbon species. Thus, the C2F radical is expected to play an important role in the combustion processes of the carbon-fluorine chemistry. Furthermore, addition of a second H2O can catalyze the reaction with the H-abstraction barrier significantly reduced to a marginally zero value (0.5 kcal/mol). This is also indicative of the potential relevance of the title reactions in the low-temperature atmospheric chemistry.
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
Wu
Gong-Bing
GB
Sun
Chia-Chung
CC