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在量子化学对SiH与H2O和H2S反应计算的基础上,运用统计热力学和Wigner校正的Eyring过渡态理论,计算了上述两反应在200～2000K温度范围内的热力学函数、平衡常数、频率因子A和速率常数随温度的变化。计算结果表明,两反应在低温下具有热力学优势,而在高温下具有动力学优势。比较两反应的计算结果发现,在相同的温度下,SiH与H2O反应比SiH与H2S反应放热较多,但速率常数却较小。SiH与H2O反应和前文报道的SiH与HF反应的比较表明,SiH与H2O反应放热较少,而且在相同温度下,速率常数也较小。
Based on the calculation of reaction between SiH and H 2 O and H 2 S by quantum chemistry, the thermodynamic function, equilibrium constant, frequency factor A and temperature of the above two reactions in the temperature range from 200 K to 2000 K are calculated by using the statistical thermodynamics and the Wigner-corrected Eyring transition state theory Rate constant changes with temperature. The calculated results show that the two reactions have the thermodynamic advantage at low temperature and the kinetic advantage at high temperature. Comparing the results of two reactions, we found that SiH reacted with H 2 O more than that of SiH and H 2 S at the same temperature, but the rate constant was smaller. The comparison of SiH with H2O and the previously reported reaction of SiH with HF shows that SiH reacts less with H2O and has a lower rate constant at the same temperature.