Theoretical Study on the Ion-pair Formation Mechanism for the Li+I_2 →Li^+ + I_2^- System  

作　　者：SUNXiao-Min FENGDa-Cheng CAIZheng-Ting 

机构地区：[1]InstituteofTheoreticalChemistry,ShandongUniversity,Jinan250100,China

出　　处：《Chinese Journal of Structural Chemistry》2004年第5期498-501,共4页结构化学（英文）

基　　金：Supported by the grants of the National Natural Science Foundation of China (No. 20173032) and Ph.D. Special Research Foundation of the Chinese Education Department

摘　　要：For the Li + I2 →Li+ + I2- system, theoretical study has been performed on the QCISD(T) level by using the ab initio method. The collision complex in ion-pair formation process was found and optimized. These results show that the crossed molecule beam (CMB) experimental phenomenon is verified and the detailed geometry is given for the first time. A mechanism for ion-pair formation was proposed in detail. The position where the collision complex occurs affects the reaction path. Specifically, the process has threshold when the collision complex appeared before the crossing point between the covalent and ionic state potential energy surfaces. On the contrary, the process has no threshold after the crossing point. Theoretically, the title system belongs to the former case.For the Li + I2 →Li+ + I2- system, theoretical study has been performed on the QCISD(T) level by using the ab initio method. The collision complex in ion-pair formation process was found and optimized. These results show that the crossed molecule beam (CMB) experimental phenomenon is verified and the detailed geometry is given for the first time. A mechanism for ion-pair formation was proposed in detail. The position where the collision complex occurs affects the reaction path. Specifically, the process has threshold when the collision complex appeared before the crossing point between the covalent and ionic state potential energy surfaces. On the contrary, the process has no threshold after the crossing point. Theoretically, the title system belongs to the former case.

关 键 词：nonadiabatic transition two-state potential energy surface ion-pair formation 

分 类 号：O614.111[理学—无机化学] O613.44[理学—化学]