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化学学报
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化学学报 ›› 2009, Vol. 67 ›› Issue (2): 122-128. 上一篇    下一篇

研究论文

OH抽提1-戊醇分子中α-H和β-H引发的大气反应机理的理论研究

赵 燕a 王 慧b 孙孝敏a 张庆竹*,a 王文兴a

  

  1. (a山东大学环境研究院 济南 250100)
    (b清华大学环境科学与工程系 北京 100080)

  • 投稿日期:2008-05-13 修回日期:2008-12-09 发布日期:2009-01-28
  • 通讯作者: 张庆竹

Theoretical Study on the Reaction Mechanism of the α-H and β-H Abstractions from 1-Pentanol by OH in Atmosphere

Zhao, Yan a Wang, Hui b Sun, Xiaomin a Zhang, Qingzhu *,a
Wang, Wenxing a
  

  1. (a Environment Research Institute, Shandong University, Jinan 250100)
    (b Environment Science and Engineering Institute, Tsinghua University, Beijing 100080)
  • Received:2008-05-13 Revised:2008-12-09 Published:2009-01-28
  • Contact: Zhang, Qingzhu

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被引次数

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采用量子化学密度泛函理论研究了OH抽提1-戊醇分子中α-H和β-H引发的大气反应的机理. 在B3LYP/6-311＋G(3df,2p)//B3LYP/6-31G(d)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, 给出了各反应通道的自由能剖面图. 计算结果表明: OH抽提1-戊醇分子中α-H和β-H引发的反应通道的主要产物分别为1-戊醛和1-丁醛; 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: 1-戊醇, 反应机理, 单分子分解, 异构化反应

The reaction mechanism of the α-H and β-H abstractions from 1-pentanol by OH radical has been studied using density functional theory at the B3LYP/6-31G(d) level. The geometries of the stationary points were optimized, and the harmonic vibration frequencies were calculated. The detailed profiles of the free energy surfaces for the reactions were constructed. The calculation results show that the main products of the α-H and β-H abstraction-initiated channels are 1-pentanal and 1-butanal, respectively. All the products from the two reaction channels can contribute to the formation of secondary organic aerosol through nucleation, hydration or absorption since their polarity and water-solubility are enhanced.

Key words: 1-pentanol, reaction mechanism, unimolecular decomposition, isomerization