Electronic structures around the local defects in all-trans-polyacetylene: An analysis by the cluster-series model

A new approach to analyze the electronic structure around the local defects in a polymer chain is developed based on the cluster-series model. In this approach, by extending the cluster molecule to both sides of the defect, the size effect on electronic structure can be estimated systematically and efficiently. Moreover, through the extension process, the periodicity of electronic structure can be extracted in the form of the periodic pattern of stationary orbitals, which are molecular orbitals unaltered by the extension of the cluster. Such periodic orbitals characterize the bulk states of periodic polymer and the energy band structure can be reconstructed from them. Illustrative analyses of some kinds of local defects in all-trans-polyacetylene are presented at the ab initio STO-3G level. The effects of local defects can be detected by the deviation from periodic bulk states. © 1993 John Wiley & Sons, Inc.