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用量子化学从头算方法对色氨酸 酪氨酸缩聚二肽体系进行电子转移动力学参数的计算。用UHF/ 6 3 1G 方法分别优化给体 ,受体和桥体的几何构型 ,用线性反应坐标构造了给体和受体分子间电子转移的双势阱 ,得到两透热势能面在Rc 约为 0处交叉 ,表明气相反应为无能垒过程。采用两态变分法 ,获得了色氨酰酪氨酸及酪氨酰色氨酸体系的分子内电子转移矩阵元VBA分别为 7.1 0J·mol-1和 5 .5 1J·mol-1。采用Marcus双球模型估算了反应的溶剂重组能。按半经典模型计算色氨酰酪氨酸及酪氨酰色氨酸体系在不同温度下的分子内电子转移速率常数
Calculation of Electron Transfer Kinetic Parameters of Tryptophan Tyrosine Polycondensation Dipeptide System by Ab Initio Quantum Chemical Method. The geometric configurations of donor, acceptor and pontic were optimized by UHF / 6 3 1G method respectively. The double-potential well of electron transfer between donor and acceptor was constructed by linear reaction coordinates. About 0 crosses, indicating that the gas phase reaction is a barrierless process. The intramolecular electron transfer matrix (VBA) of tryptophan tyrosine and tyrosyltryptophan were obtained by two-state variational method, which were 7.1 0J · mol-1 and 5.51J · mol-1, respectively. The solvent reorganization energy of the reaction was estimated using the Marcus double sphere model. According to the semiclassical model, the intramolecular electron transfer rate constant of tryptophanotyrosine and tyrosyltryptophan at different temperatures