非绝热电子转移动力学模型及O2O2→O2O2研究

A Kinetic Model of Nonadiabatic Electron Transfer andIts Application to O_2O_2￣-→O_2￣-O_2

描述非绝热电子转移的半经典模型，揭示了对称双势阱非绝热电子转移的过渡态能垒与Ａｒｒｈｅｎｉｕｓ活化能关系的一些新特征。在４－３１Ｇ加负离子ｓｐ弥散函数水平上优化了共线反应的反应物、络合物和过渡态的构型，成功地进行了电子定域ＵＨＦ诱导自洽场计算，获得电子转移矩阵元ＶＡＢ为７．ＯｋＪ／ｍｏｌ，活化能垒Ｅｃ为２８．４ｋＪ／ｍｏｌ，３００Ｋ时反应速率常数ｋ为９．２×１０８／ｓ，讨论了理论模型及计算结果。

the semiclassical model for nonadiabatic electron transfer has been described.Some new features for the relations between the energy barrier (E_c) at the crossing point and the activation energy(E_a) in the Arrhenius rate law have been revealed.The complex, reac tants, and the transition state for the colinear reaction have been optimized at 4-31G augmented with a set of anion diffuse functions. After a successful UHF SCF calcula tion due to a electron-located initial guess, the authors have obtained the electron transfer matrix element V_(AB)= 7. 0 kJ/mol , the energy barrier E_c= 28. 4 kJ/mol , the rate constant k=9. 2 × 10￣8/s at 300 K. The discussions for the theoretical model and the calculated results have been made.