硅锗酞菁聚合物的电子结构

Electronic Structures of Si- and Ge-phthalocyaninato Polymers

在自洽场晶体轨道法全略微分重叠（SCF CNDO／2－CO）水平上对氧桥和硫桥一维链硅锗酞菁聚合物的能带结构和电子特性进行了研究，探讨了堆积酞菁环间交错角以及中心原子和桥原子的变化对电子特性的影响．计算结果表明，除前线带宽外，交错角变化对所研究的聚酞菁电子特性影响不大．晶体轨道分析表明，氧桥聚酞菁电荷载流子主要通过垂直酞菁环π轨道的纵向重叠导电通路流动，而硫桥聚酞菁导带电子还可经中心原子和桥原子的d轨道重叠通路迁移．

Abstract SCF-CNDO/2-CO method is used to study the band structures and electronic properties of one-dimensional phthalocyaninato (Pc) polymers [MPcX],(M=Si, Ge ; X=O, S). It has been discussed that the electronic properties vary with the kinds of atoms and the staggering angle between neighboring rings. The calculated results show that the variation of the staggering angle has not any strong effect on electronic properties of polymers except for the frontier bandwidth. The analysis of crystal orbitals shows that in [MPcO]n conduction pathway of charge-carrier is mainly composed of the overlaps of orbitals of phthalocyanine ring; while in [MPcS]n, the electrons in conduction band can also move along the polymer chain through the d-orbital overlaps of central and bridge atoms.