酞菁金属络合物电子能级计算的一种新方法——自由电子环模型基础之上的微扰论

A New Model on Study of the Electronic Structure and Spectra of Metal Phthalocyanine

本文给出一种新的处理金属酞菁电子结构的方法——在以自由电子环模型处理中心大环共轭π电子的基础,把共轭环上π电子之间的关联效应和四个外接苯环的作用作为微扰处理,对于四个苯环的微扰作用采用偶极子近似;对于π电子之间的关联作用,取旋转对称的有效势形式。计算得到了较卟啉红移的Q带和较卟啉兰移的B带以及Q带的跃迁矩,与实验结果基本相符。后还讨论萘酞菁的光谱。

A new model is presented to deal with the electronic structure and spectra of mctal phthalocyanine by treating the macrocycle π-electron with the free electron ring model and the correlation of π-electrons and the interaction of the external benzene rings (with macrocycle) as perturbation. These benzene rings are approximated as dipoles, the Q-band obtained is red shifted from that of porphyrin; the B-band is blue shifted and the transition moment of Q-band is different from zero. These results are in rather good agreement with the experimental data. Finally we have discussed qualitatively the electronic structure of naphthalocyanine.