气相中Re^+与C_2H_4连续反应机理的理论研究

Theoretical Study on Continuous Reaction Mechanism of Re^+ and C_2H_4 in Gas Phase

采用密度泛函理论B3LYP方法研究基态下Re^+与C_2H_4连续反应的机理.Re^+与C_2H_4的反应是一个典型的插入-消除机制,第一步反应(形成IM_1的过程)放出的热量高达416.64kJ/mol.Re^+与C_2H_4一旦反应,整个反应就能自动进行下去,这为高能材料的研究提供了参考.Re^+与C_2H_4生成Re(C_2H_2)^+,放出1分子的H_2,反应生成的产物继续与C_2H_4反应,随着吸附C_2H_4的增多,吸附变得越来越难,反应决速步骤的能垒也越来越高,C-H键的断裂随之变得越来越困难,H_2也越来越难形成.当吸附到第4个C_2H_4时,C-H键已经很难断裂.

The continuous reaction mechanism of Re^＋ and C2H4 of ground state is under studied with density functional theory B3LYP.The reaction of Re^＋ and C2H4 is a typical inserting eliminating mechanism,which gives out heat as high as 416.64kJ/mol.The whole reaction will conduct automatically once Re^＋ reacts with C2H4,which provides foundation for the study of energetic materials.The reaction of Re＋and C2H4 produces Re（C2H2）^＋,and releases 1 molecular H2,the product of reaction continues to react with C2H4,and the adsorption becomes harder,the energy banner of reaction rate determining step higher,the breakageof C-H keyharder,and the formation of H2 more difficult as the increasing of adopted C2H4. C-H key is very difficult to be broken when the fourth C2H4 is under adsorption.