Accession Number : ADA330129

Title :   Electronic Structure of Pyridine-Based Polymers.

Descriptive Note : Technical rept.,

Corporate Author : OHIO STATE UNIV COLUMBUS DEPT OF PHYSICS

Personal Author(s) : Blatchford, J. W. ; Gustafson, T. L. ; Epstein, A. J.

PDF Url : ADA330129

Report Date : 20 SEP 1997

Pagination or Media Count : 49

Abstract : We present the results of semiempirical quantum chemical calculations on oligomers of poly (p-pyridyl vinylene) (PPyV) and poly (p-pyridine) (PPy). The presence op a nitrogen heteroatom in the conjugated backbone of these polymers presents a severe breaking of both spatial and charge conjugation symmetry (CCS), and the addition of nonbonding (n) orbitals has potentially major effects on the photophysics of these systems. Geometries are optimized at the PM3 Hartree-Fock level for neutral, singly charged and doubly charged oligomers. We find that the geometric distortions associated with polaron formation are centered on the vinylene linkages in PPyV-based systems and on the interring bonds in the ppy.based systems. We discuss the electronic structure at the PM3 level applying configuration interaction between singly excited states (SCI), and we demonstrate that the lowest-lying (n approaches (pi)*) states of the ideal polymer chain are well above the lowest states, predicting strong fluorescence in these systems. Deviations from ideal geometry, however, can lead to substantial mixing of the manifolds, thereby altering this conclusion. We calculate absorption spectra for neutral, singly charged (polaron) doubly charged (bi-polaron) and triplet state oligomers using the INDO/SCI technique. For PPyV comparison of oligomers with differing spatial symmetry allows the isolation of the effects of CCS breaking. All calculated spectra are in good agreement with experimental results and indicate that the symmetry breaking due to the nitrogen heteroatom is weak.

Descriptors :   *POLYMERS, *ELECTRONIC STATES, *PYRIDINES, *HARTREE FOCK APPROXIMATION, SPATIAL DISTRIBUTION, QUANTUM CHEMISTRY, INTERACTIONS, ISOLATION, GEOMETRY, QUANTUM ELECTRONICS, ABSORPTION SPECTRA, PHASE DISTORTION, LIGHT EMITTING DIODES, QUANTUM STATISTICS.

Subject Categories : Polymer Chemistry
      Quantum Theory and Relativity

Distribution Statement : APPROVED FOR PUBLIC RELEASE