Acta Chimica Sinica ›› 2005, Vol. 63 ›› Issue (3): 196-202. Previous Articles     Next Articles

Original Articles

HO2自由基与NO2反应通道的理论研究

白洪涛,黄旭日*,魏志钢,李吉来,孙家钟   

  1. (吉林大学理论化学研究所理论化学计算国家重点实验室 长春 130023)
  • 收稿日期:2004-08-05 修回日期:2004-10-29 出版日期:2005-02-14 发布日期:2010-12-10
  • 通讯作者: 黄旭日

Theoretical Study on the Reaction of HO2 Radical with NO2 by Density Functional Theory Method

BAI Hong-Tao,HUANG Xu-Ri*, WEI Zhi-Gang, LI Ji-Lai,SUN Jia-Zhong   

  1. (Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemis-try,
    Jilin University, Changchun 130023)
  • Received:2004-08-05 Revised:2004-10-29 Online:2005-02-14 Published:2010-12-10
  • Contact: HUANG Xu-Ri

Using the density functional theory (DFT/B3LYP) method, the reaction of HO2 radical with NO2 was studied. The potential energy surfaces (PES) of the HO2+NO2 reaction were calculated at B3LYP/6-311G** and CCSD (T)/6-311G** (single-point) levels of the theory. It is shown that the direct H-extrusion reaction mechanism is the main reaction channel on the singlet PES for the title reaction, namely, a direct H-shift from the HO2 radical to the N atom of the NO2 molecule to form the product P1 (HNO23O2). Another favorable reaction channel on the singlet PES involves that the end O atom of the HO2 radical attacks on the N atom of the NO2 molecule, forming the isomer 1 (HOONO2), then H-shift follows, producing P2 (trans-HONO+3O2). Both of the reaction channels mentioned above are exothermic with the energy of 90.14 and 132.52 kJ•mol-1, re-spectively.

Key words: DFT, potential energy surface, HO2+NO2, reaction channel