用从头算法计算气相条件下金属-苯反应体系中电子转移反应的量子效应

Quantum effect of electron transfer reaction for metal-benzene interaction system in the gas phase:an ab initio computation

提出了一种求算金属 -苯和金属离子 -苯配合物电子转移反应的 Franck- Condon( FC)因子的从头算法 ,并计算了金属 -苯配合物的振动频率 .在振动频率比热能 ( k T)低 ,并且键长的变化小于从反应物到产物间距离的情况下 ,此法算出的 FC因子与经典和半经典方法的计算结果相吻合 .本研究的电子转移反应是在气相条件下进行的 ,可以忽略电子转移反应的外氛影响 ,用量子力学的方法来描述更为合适 .

An ab initio computation of the Franck Condon(FC)factor for the electron transfer(ET) reactions between metal benzene and metal ion benzene complexes is presented.The vibrational frequencies of the metal benzene complexes are calculated.The FC factors computed by using ab initio method are agree with the classical and semiclassical results,in case of the vibrational frequency lower than the heat energy kT,and the change of the bond length is less from the reactant to the product.The ET reaction is in the gas phase,the influence of outersphere on the ET reaction can be neglected.The ET reaction described by using quantum mechanic is more suitable.