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化学学报
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化学学报 ›› 2005, Vol. 63 ›› Issue (3): 196-202. 上一篇    下一篇

研究论文

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)
  • 投稿日期:2004-08-05 修回日期:2004-10-29 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 Published:2010-12-10
  • Contact: HUANG Xu-Ri

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应用密度泛函理论DFT/B3LYP对HO2＋NO2反应进行了研究, 在B3LYP/6-311G**和CCSD(T)/6-311G**水平上计算了HO2自由基与NO2分子反应的单重态和三重态反应势能面, 计算结果表明, 单重态反应势能面中的直接氢抽提反应机理是此反应的主要反应通道, 即HO2自由基的氢原子转移到NO2分子的氮原子上形成产物P1 (HNO2＋3O2), 另一个可能的反应通道是单重态反应势能面上HO2中的端位氧原子进攻NO2分子中的氮原子形成中间体1 (HOONO2), 接着中间体1 (HOONO2)经过氢转移形成产物P2 (trans-HONO＋3O2), 以上两个反应通道都是放热反应通道, 分别放热90.14和132.52 kJ•mol－1.

关键词: 密度泛函理论, 势能面, HO2＋NO2, 反应通道

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 (HNO2＋3O2). 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