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化学学报
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化学学报 ›› 1996, Vol. 54 ›› Issue (7): 632-637. 上一篇    下一篇

研究论文

CH(^4∑^-)+H2O→CH2(^3B1)+OH的直接动态学研究

马思渝;刘若庄   

  1. 北京师范大学化学系
  • 发布日期:1996-07-15

Studies on the direct dynamics of the reaction CH(^4∑^-)+H2O→CH2(^3B1)+OH

MA SIYU;LIU RUOZHUANG   

  • Published:1996-07-15

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用从头算方法计算了反应CH(^4∑^-)+H2O→CH2(^3B1)+OH的反应途径。在此基础上, 计算沿反应途径的动态学性质和正则变分过渡态理论的速率常数, 并进行隧道效应校正。结果表明, 电子相关能对反应活化位垒影响较大; 反应存在返回效应和隧道效应, 用正则变分过渡态方法和小曲率近似的隧道校正是有效的。

关键词: 从头计算法, 反应速度常数, 过渡态理论, 亚稳态, 次甲基

The reaction path of the reaction CH(^4∑^-)+H2O→CH2(^3B1)+OH is traced with Fukui's theory of intrinsic reaction coordinate by using ab initio MO method with gradient technique. On the basis, the dynamical properties along the reaction path and CVT (canonical variational theory) rate constants with correction of tunneling effect are investigated by reaction path Hamiltonian theory and variational transition state theory. The results show that the effects of electron correlation energy to the activation barrier are notable, the recrossing and tunneling effects exist and the corrections by means of CVT method and small curvature approximation method respectively are efficient.

Key words: AB INITIO CALCULATION, REACTION RATE CONSTANT, TRANSITION STATE THEORY, METASTABLE STATES, METHENYL-

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