LiX(X=H,D,T)与水的反应机理和动力学研究

Mechanism and Kinetics of LiX(X=H,D,T)+H_2O Reaction

采用Gaussian03软件包中的量子化学从头计算法,在6-311G(d)水平上,用量子化学MP2方法研究了Li X(X=H,D,T)与水的反应,计算了反应体系最低势能面上各驻点的构型参数、振动频率和能量,全面研究了反应机理;利用经典过渡态理论,考虑量子化矫正,计算了反应的速率常数。计算结果显示,LiH(LiD、LiT)与水的反应受温度影响很大,温度越低反应速率常数越小。

The reaction mechanism of LiX（X=H,D,T） with H2O was investigated at MP2/6-311G（d） level using ab initio quantum chemistry in Gaussian03 software.The equilibrium geometries,harmonic frequencies and energy of various stationary points on the potential energy surfaces were calculated in the lowest singlet states.Considering the quantum correction,the reaction rate constants were calculated using classical transition state theory.The results show the reaction of LiH（LiD,LiT） with H2O was considerably dependent on temperature that it is lower,the reaction rate constants are smaller.