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化学学报
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化学学报 ›› 2009, Vol. 67 ›› Issue (18): 2102-2108. 上一篇    下一篇

研究论文

CH3SS与XO (X＝F, Cl, Br)反应过程的电子密度拓扑研究

李晓艳, 孟令鹏, 曾艳丽， 郑世钧   

  1. (河北师范大学计算量子化学研究所 石家庄, 050016）)
  • 投稿日期:2008-06-26 修回日期:2008-10-28 发布日期:2009-12-31
  • 通讯作者: 郑世钧

Topological Analysis of Electronic Density on the Reactions of CH3SS with XO (X＝F, Cl and Br)

Li, Xiao-Yyan, Meng, Ling-Ppeng, Zeng, Yan-lili, Zheng, Shi-Jjun*   

  1. (Institute of Computational Quantum Chemistry, College of chemistryChemistry, Hebei Normal University, Yuhua Road, Shijiazhuang, 050016)
  • Received:2008-06-26 Revised:2008-10-28 Published:2009-12-31
  • Contact: Zheng, Shi-Jjun

利用MP2/6-311＋＋G(d,p)//B3LYP/6-311＋＋G(d,p)对CH3SS与XO (X＝F, Cl, Br)的反应机理进行了研究. 着重从电子密度拓扑分析角度讨论了化学键的生成和断裂. 计算结果表明单线态反应为主要反应通道, 且由于该通道的反应能垒低、放热明显, 说明CH3SS与XO在大气中比较容易进行. 电子密度拓扑分析表明, 在单线态抽氢反应通道中存在着四元环状过渡结构, 随着反应进行, 此四元环状过渡结构通过一个T-型结构变为三元环状过渡结构, 最后环状结构消失得到产物.

关键词: 电子密度拓扑分析；, 结构过渡区；, 结构过渡态

The reaction mechanism of CH3SS with XO (X＝F, Cl, Br) have has been studied at MP2/6-311＋＋++G(d,p)//B3LYP/6-311＋＋++G (d, p) level. The breakage and formation of the chemical bonds in the main reaction channel have been discussed by the topological analysis method of electronic density. The calculated results shows that because of the low energy barrier and high exothermicity, the reaction of CH3SS with XO could occur easily in the atmosphere. Furthermore, the topological analysis shows that a four-membered- ring structure exists in the hydrogen abstract channel, it turns to a three-membered -ring structure by the a T-shaped structure, then the ring structure disappeared disappears and the products are gained.

Key words: topological analysis of electronic density, structure transition region, structure transition state