Ab InitioCalculation of the Electronic and Optical Excitations in Polythiophene: Effects of Intra- and Interchain Screening

Abstract

We present an ab initio calculation of the electronic and optical excitations of an isolated polythiophene chain as well as of bulk polythiophene. We use the $\mathrm{GW}$ approximation for the electronic self-energy and include excitonic effects by solving the electron-hole Bethe-Salpeter equation. The inclusion of interchain screening in the case of bulk polythiophene drastically reduces both the quasiparticle band gap and the exciton binding energies, but the optical gap is hardly affected. This finding is relevant for conjugated polymers in general.