化学学报 ›› 2011, Vol. 69 ›› Issue (17): 1965-1972. 上一篇    下一篇

研究论文

大气中芳樟醇与臭氧反应机理的理论研究(I)

孙廷利1,王玉东1,张晨曦1,孙孝敏1,2,胡敬田*,1   

  1. (1山东大学环境研究院 济南 250100)
    (2中国科学院兰州化学物理研究所固体润滑国家重点实验室 兰州 730000)
  • 收稿日期:2011-01-11 修回日期:2011-04-30 出版日期:2011-09-14 发布日期:2011-05-16
  • 通讯作者: 孙孝敏 E-mail:sxmwch@sdu.edu.cn
  • 基金资助:

    无盐囊泡相结构的实验与分子动力学模拟理论研究;持久性有机污染物的典型环境过程以及构效关系研究;二噁英(Dioxin)降解的量子化学研究和分子模拟

Theoretical Study on the Reaction Mechanism of the Linalool with Ozone in Atmosphere

Sun Tingli1 Wang Yudong1 Zhang Chenxi1 Sun Xiaomin1,2 Hu Jingtian*,1   

  1. (1 Environment Research Institute, Shandong University, Jinan 250100)
    (2 State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Science, Lanzhou 730000)
  • Received:2011-01-11 Revised:2011-04-30 Online:2011-09-14 Published:2011-05-16
  • Contact: SUN Xiao-Min E-mail:sxmwch@sdu.edu.cn

采用密度泛函理论研究了大气中芳樟醇臭氧化反应机理. 在B3LYP/6-31G*水平上对该反应体系的反应物、中间体、过渡态及产物进行了几何构型优化和频率计算, 在B3LYP/6-311+G(3df,2pd)水平下进行单点能量计算, 构筑了反应的势能剖面. 对反应中间体与H2O和NO可能的氧化机理进行了详细的描述. 并对转化过程中各竞争反应的反应势垒、反应热和Gibbs自由能等物理化学参数进行了详细分析. 生成的产物极性和水溶性增强, 易通过成核、水合或吸附反应形成二次有机气溶胶.

关键词: 芳樟醇, 臭氧化, 反应机理, 二次有机气溶胶

The reaction mechanism of the linalool with ozone in atmosphere has been studied using density functional theory. The geometries of the stationary points were optimized, and the harmonic vibration frequencies were calculated at the B3LYP/6-31G(d) level. The single point energies of the stationary point were calculated at the B3LYP/6-311+G(3df,2pd) level and the detailed profiles of the potential energy surfaces for the reactions were constructed. The potential oxidation mechanisms of the intermediates with H2O or NO were discussed in detail. The physicochemical parameters of the competing reaction channels including reaction barrier, enthalpy change, and Gibbs free energy change have been analyzed. Most of the products can contribute to the formation of secondary organic aerosol through nucleation, hydration or absorption since their polarity and water-solubility enhance.

Key words: linalool, ozonization, reaction mechanism, secondary organic aerosol