Theoretical study on reaction mechanism of the CF radical with nitrogen dioxide

✍ Scribed by Yu-guo Tao; Yi-hong Ding; Jian-jun Liu; Ze-sheng Li; Xu-ri Huang; Chia-Chung Sun

• Publisher: John Wiley and Sons
• Year: 2001
• Tongue: English
• Weight: 308 KB
• Volume: 22
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.1141

✦ Synopsis

Abstract

The singlet potential energy surface of the [CFNO~2~] system is investigated at the B3LYP and CCSD(T) (single‐point) levels to explore the possible reaction mechanism of CF radical with NO~2~. The top attack of C‐atom of CF radical at the N‐atom of NO~2~ molecule first forms the adduct isomer FCNO~2~ 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 P~1~, P~2~, and P~3~ to take secondary dissociation to the final product P~12~ F+CO+NO. Another energetically allowed channel is formation of product P~4~ ^1^NF+CO~2~, 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+NO~2~. 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. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1907–1919, 2001