Valence effective Hamiltonian (VEH) calculations are performed on a number of sulfur containing organic conjugated polymers of interest to the conducting polymers area. Theoretical results for parameters related to conductivity such as ionization potentials, bandwidths, and bandgaps are presented. Systems considered include various derivatives of poly (p-phenylene sulfide), polybenzothiophene, and polythiophene, as well as potentially interesting compounds such as polythieno [3,2-b] thiophene and polyvinylene sulfide. The electronic structure description afforded by the VEH method for sulfur containing polymers is demonstrated to be of the same quality as that presented previously for hydrocarbon polymers. In particular, for ionization potentials, good agreement with available experimental data on poly (p-phenylene sulfide) and polybenzothiophene is obtained, after scaling downward the VEH values by a 1.9 eV polarization correction. The comparison between the theoretical and experimental XPS spectra for polybenzothiophene is excellent with use of the same energy scaling factor previously employed for polyacetylene, poly(p-phenylene), and poly(p-phenylene sulfide). These results, in conjuction with previous results obtained on hydrocarbon polymers, lend confidence in the predictive capabilities of this purely theoretical technique. Calculations show that polyvinylene sulfide, as yet unsynthesized, should display very promising characteristics as a conducting polymer.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry