Valence effective Hamiltonian study of the electronic structure of poly(p-phenylene) and poly(p-phenylene sulfide)

Abstract

The parametrization of atomic potentials for sulfur is presented in the framework of the valence effective Hamiltonian (VEH) technique for polymers. The VEH method is applied to band structure and density of states calculations on poly(p-phenylene) and poly(p-phenylene sulfide), compounds of interest with regard to the conducting polymers area. The quality of the electronic structure description afforded by the VEH technique is demonstrated via a comparison of experimental XPS spectra for these polymers with spectra predicted theoretically. The ionization potential of poly(p-phenylene sulfide) is predicted to be 0.7 eV higher than poly(p-phenylene) in good agreement with experimental estimates.