LiH和LiT与H_2O反应机理研究

Study on Reaction Mechanisms of LiH and LiT With H_2O

氢材料在微量H2O、CO2、O2和N2存在下可能发生物理化学反应,使材料的物理品位下降。由于反应过程十分复杂,很难从实验上准确获取这类反应的最佳通道和具体产物信息,因此,从理论上研究氢材料分子的物理化学性质及其化学反应机制,了解化学反应过程具有十分重要的意义。本文使用Gaussian03软件包和Gaussview工具软件,在6-311G(d)全电子基函数水平上,应用二阶微扰理论优化得到了6 LiH、6 LiT与H2O反应的中间体、过渡态及产物的结构,总能量,振动频率和零点能等。通过计算发现6LiH、6LiT均只有1个反应通道,6LiH与H2O反应的焓变、活化能和反应速率常数分别为-156.99kJ/mol、8.95kJ/mol和3.75×1010(mol·dm-3)-1/s,6 LiT与H2O反应的焓变、活化能和反应速率常数分别为-159.02kJ/mol、9.92kJ/mol和1.72×1010(mol·dm-3)-1/s。

When trace H2O,CO2,O2 and N2in hydrogen materials,physical and chemical reactions between them may occur,and the physical quality reduces.Due to the complex reaction process,it is difficult to obtain the best channel and specific product information from experiments.Therefore,it is very important to research physical and chemical properties and chemical reaction mechanism theoretically.At the full electron6-311G（d）base sets level,the geometry configurations of intermediates,transition state and products,the total energy,the vibration frequency,the zero point energy and so on were acquired by the second-order perturbation method with the help of Gaussian03 software package and Gaussview tool software.The results of calculation show that6 LiH and 6LiT have only one reaction channel.The enthalpy,activation energy and reaction rate constant of the reaction between 6LiH and H2O are-156.99kJ/mol,8.95kJ/mol and 3.75×1010（mol·dm-3）-1/s,respectively.The enthalpy,activation energy and reaction rate constant of the reaction between 6LiT and H2O are-159.02kJ/mol,9.92kJ/mol and 1.72×1010（mol·dm-3）-1/s,respectively.