溶液中M(H_2O)_6^(2+/3+)(M=V,Cr,Mn,Fe,Co)自交换电子转移体系内层重组能和活化能的理论研究

Theoretical Study of the Inner\|sphere Reorganization \=Energy and Activation Energy of Self\|exchange \=Electron Transfer Reaction for M(H\-2O)\+\{2+/3+\}\-6\=(M=V, Cr, Mn, Fe and Co) Systems

通过建立电子转移过程的活化模型和重组模型，提出了用量子化学从头算方法研究电子转移过程内层重组能和活化能的新方法．在ＵＭＰ２／６－３１１Ｇ水平上获得了５对过渡金属水合离子体系Ｍ（Ｈ２Ｏ）２＋／３＋６（Ｍ＝Ｖ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ）自交换反应的内层重组能和活化能。

The activation model and reorganization model of electron transfer process are presented respectively in terms of the definitions of activation energy and reorganization energy. A new method is presented for calculating the inner\|sphere activation energy and reorganization energy of self\|exchange electron transfer reaction between transition metal complexes in aqueous solution by using \%ab initio\% calculation. \%Ab initio\% calculations are applied to low\|lying state M(H\-2O)\+\{2+/3+\}\-6(M=V, Cr, Mn, Fe and Co) system at the UMP2 level using \{6\|311G\} basis set. The inner\|sphere reorganization energy and activation energy of these reaction systems in the electron process are obtained and are in good agreement with prediction of Marcus electron transfer theory. \=