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化学学报
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化学学报 ›› 1990, Vol. 48 ›› Issue (2): 105-109.    下一篇

研究论文

二硅烯异构化反应的理论研究, 从头等水平上的动力学, 热力学分析

居冠之;马万勇;邓从豪   

  1. 山东大学理论化学研究所
  • 发布日期:1990-02-15

Theoretical study on the singlet disilene-silylsilylene isomerization: analyse for dynamics and thermodynamics at ab initio level

JU GUANZHI;MA WANYONG;DENG CONGHAO   

  • Published:1990-02-15

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578

本文在从头算水平上计算了二硅烯HXSi-SiH2(X=H,D)异构化反应的反应物、产物及过渡态构型的能量、谐振动频率和反应活化能等,又计算了反应的热力学函数变化, 平衡常数及速率常数, 结果表明,该异构化反应是放热的, 且可自发进行, 结论与Newman的实验事实相符合, 值得注意的是, 零点能校正对该异构化反应的计算有改进。

关键词: 平衡常数, 动力学分析, 从头计算法, 异构化反应, 反应速度常数, 硅烯, 二硅烷 P, 热力学分析

The title isomerization of disilene, HXSi:SiH2 (X = 3h, 3d), was studied at the ab initio level. The energies of reactant, product, and transition state, their harmonic vibrational frequencies, and barrier energy were calculated The change in thermodn. functions, the equilibrium constant, and the rate constant for the isomerization reaction were also computed. The reaction is exothermic and spontaneous. This conclusion agrees with G. C. Newman et al. (1979) experimental results.

Key words: EQUILIBRIUM CONSTANT, KINETIC ANALYSIS, AB INITIO CALCULATION, ISOMERIZATION REACTION, REACTION RATE CONSTANT, SILYLENE, DISILANE P, THERMODYNAMIC ANALYSIS

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