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化学学报
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化学学报 ›› 2002, Vol. 60 ›› Issue (11): 1909-1914. 上一篇    下一篇

研究论文

氮原子与卤代甲烷反应的直接氢抽提过程研究

周晓国;李江;俞书勤;马兴孝   

  1. 中国科学技术大学化学物理系,合肥(230026)
  • 发布日期:2002-11-15

Study on the Hydrogen Abstraction Reaction between N(~4S) and CH_3X (X = H, F, Cl)

Zhou Xiaoguo;Li Jiang;Yu Shuqin;Ma Xingxiao   

  1. Laboratory of Bond Selective Chemistry, Department of Chemical Physics, University of Science and Technology of China,Hefei(230026)
  • Published:2002-11-15

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547

被引次数

5 | 2

利用B3LYP理论研究了N(~4S)+CH_3X(X = H, F, Cl)反应体系的直接氢抽提过 程，分别得到了各反应物、产物和过渡态的优化构型和谐振频率。同时应用了6- 31G(d), 6-311+G(d,p)和6-311+ + G(2d,2p)基组，考察其大小对反应体系中各物 种构型及能量的影响。理论计算表明，随着基组的增加，反应势垒逐渐降低，反应 吸热减少。对比取代甲烷的情形，结果表明反应过程中卤素原子具有典型的诱导效 应，降低了抽提势垒。

关键词: 氮原子, 卤代烃, 甲烷 P, 过渡态

Hydrogen abstraction reaction between N(~4S) and CH_3X (X = H, F, Cl) is explored using the B3LYP method. Optimized geometries and harmonic frequencies of reactants, products and transition states are obtained. The 6-31G(d), 6-311+G(d,p) and 6-311++G(2d, 2p) basis sets are employed in present calculations, in order to investigate effects of the size of the basis sets. Results show that the activation barriers and reaction endothermic values are reduced with increasing of the basis sets. Additionally, compared with reactions involving CH_4, CH_3F and CH_3Cl, the present results suggest that the inductive effect of halogen atom lowers the activation barrier for hydrogen abstraction.

Key words: NITROGEN ATOM, HALOHYDROCARBON, METHANE P, TRANSITION STATE

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