NH_3/NH_3^+体系电子转移性的黄金规则研究

Golden-rule Study of Electron Transfer Reactivity of NH_3/NH_3^+ System

用密度泛函理论 (B3P86 ,B3LYP)在 6 31G ,6 311+G 基组水平上和从头算方法 [MP2 (FULL) /6 311+G ]优化了NH3 和NH3 + 以及复合物 (NH3 …NH3 ) + 的几何构型 ,计算了体系稳定化能 .然后用MP2 (FULL) /6 311+G 方法扫描势能面找出不同N N接触距离的活化态体系的能量、活化能、耦合矩阵元 ,利用黄金规则计算出不同的N N接触距离的电子转移速率 .并讨论了活化态体系的能量、活化能、耦合矩阵元和Franck Condon因子及电子转移速率与接触距离的依赖关系 .进一步验证了黄金规则应用于电子转移反应的正确性 .

Density function theory (B3P86, B3LYP) at 6-31G* and 6-311 + G* basis set levels and ab initio calculation [MP2(FULL)] at 6-311 + G* basis set level are used to optimize the molecular structures of NH3, NH3+ and the complex (NH3...NH3)(+). The stabilization energy of this system is calculated. Then at 6-311 + G* basis set level MP2(FULL) method is used to scan the potential energy surface of different N-N contact distance in order to obtain the energies, activation energies, coupling matrix elements and Franck-Condon factors of this system. The electron transfer rate is calculated by using the Golden-rule scheme. Finally, the contact distance dependence of these kinetics quantities is discussed. The rationality of Golden-rule has been justified for the application to ET system once again.