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1697752 
Journal Article 
Theoretical study on reaction mechanism of the CF radical with nitrogen dioxide 
Tao, YG; Ding, YH; Liu, JJ; Li, ZS; Huang, XR; Sun, CC 
2001 
Yes 
Journal of Computational Chemistry
ISSN: 0192-8651
EISSN: 1096-987X 
22 
16 
1907-1919 
WOS:000171989900005 
The singlet potential energy surface of the [CFNO2] system is investigated at the B3LYP and CCSD(T) (single-point) levels to explore the possible reaction mechanism of CF radical with NO2. The top attack of C-atom of CF radical at the N-atom of NO2 molecule first forms the adduct isomer FCNO2 1 followed by oxygen-shift to give trans-OC(F)NO 2 and then to cis-OC(F)NO 3. Subsequently, the most favorable channel is a direct dissociation of 2 and 3 to product P-1 FCO + NO. The second and third less favorable channels are direct dissociation of 3 to product P-2 FNO + CO and isomerization. of 3 to a complex NOF...CO 4, which can easily dissociate to product P-3 FON + CO, respectively. The large exothermicity released in these processes further drives most of the three products P1, P2, and P3 to take secondary dissociation to the final product P-12 F + CO + NO. Another energetically allowed channel is formation of product P-4 (NF)-N-1 + CO2, yet it is much less competitive than P-1, P-2, P-3, and P-12. The present calculations can well interpret one recent experimental fact that the title reaction is quite fast yet still much slower than the analogous reaction CH + NO2. Also, the results presented in this article may be useful for future product distribution analysis of the title reaction as well as for the analogous CCl and CBr reactions. (C) 2001 John Wiley & Sons, Inc. 
theoretical calculations; reaction mechanism; potential energy surface (PES); fluorocarbon radical (CF); nitrogen dioxide (NO2)