Chain-Length Dependence of Electronic and Electrochemical Properties of Conjugated Systems: Polyacetylene, Polyphenylene, Polythiophene, and Polypyrrole

Jean-Luc Bredas*, R. Silbey, D. S. Boudreaux, R. R. Chance

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

1095 Scopus citations

Abstract

he valence effective Hamiltonian (VEH) technique is used to compute ionization potentials, optical transition energies, and electron affinities of oligomers and polymers in four conjugated systems: polyacetylene, poly(p-phenylene), polythiophene, and polypyrrole. The theoretical results compare very favorably with experimental data on gas-phase ionization potentials, optical absorption, and electrochemical redox potentials. The latter case is especially important, and the calculated oxidation and reduction potentials are in remarkably good agreement with experiment. For polyacetylene the predicted oxidation potential is 0.4 V vs. SCE, and the predicted reduction potential is -1.1 V, both of which are in good agreement with experimentally observed oxidation and reduction onsets. In these systems, the electronic and electrochemical properties predicted by VEH theory for the oligomers extrapolate to those of the polymer with an inverse chain-length dependence.

Original languageEnglish (US)
Pages (from-to)6555-6559
Number of pages5
JournalJournal of the American Chemical Society
Volume105
Issue number22
DOIs
StatePublished - Oct 1 1983

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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