We present ab initio Hartree-Fock and valence effective Hamiltonian (VEH) calculations on polyparaphenylene, polypyrrole, and polythiophene dimers and polymer chains. These polymeric materials are among the most studied compounds in the field of conducting polymers. We examine, as a function of the torsion angle between consecutive rings, the evolution of electronic properties such as ionization potential, bandgap and width of the highest occupied bands and of the carbon-carbon bond length between rings. This investigation is motivated by the fact that many derivatives of these compounds have substituents that lead to an increase of the torsion angle between adjacent rings, as a result of steric interactions. As expected, on going from a coplanar to a perpendicular conformation, the ionization potential and bandgap values increase and the width of the highest occupied bands decreases. This makes it more difficult to ionize or reduce the polymer chains and can result in achieving lower maximum conductivities on doping. However, since the evolution of the electronic properties is found to follow a cosine law (related to the decrease of the overlap between the π orbitals on adjacent rings), the modifications up to a ∼40° torsion angle are not very large. For instance, in all three polymers, the ionization potential value for a 40° torsion angle is about 0.4 eV larger than the coplanar conformation value. Therefore, substituents that lead to torsion angles between consecutive rings smaller than 40° are quite acceptable. Finally we discuss the importance, for the substituted compounds, of the possibility of achieving a coplanar conformation upon doping, in order to permit high intrachain mobilities of charge carriers such as bipolarons.
ASJC Scopus subject areas
- General Physics and Astronomy
- Physical and Theoretical Chemistry