Thiophene-Furan oligomers: Beyond-DFT Study of Electronic and Optical Properties

TL;DR

This study uses advanced quantum chemical methods to analyze the electronic and optical properties of thiophene-furan oligomers, revealing their potential for photovoltaic applications with promising optical transition energies and ionization potentials.

Contribution

It provides a comprehensive theoretical analysis of thiophene, furan, and thienylfuran oligomers using beyond-DFT methods, highlighting structural and electronic features relevant for photovoltaics.

Findings

Optical transitions reach ~3 eV at tetramer length.

Ionization potentials are around 7 eV.

Planar and torsionally twisted conformations depend on unit sequencing.

Abstract

Thiophene oligomers are an important class of organic materials for photovoltaic applications, owing to their unique optoelectronic properties. Recently it was suggested that incorporation of furan units to the thiophene chains, maintaining the chain structure, namely thienylfuran linear oligomers, can bring improvements to the final material. In this work, we present a theoretical study of thiophene, furan and thienylfuran short chains, up to 4 units. Structural and electronic properties were obtained using Hartree-Fock (HF) and Density Functional Theory (DFT) calculations plus beyond mean-field methodologies, specifically Second-order M\"oller-Plesset perturbation theory on HF (HF-MP2) and many-body perturbation theory by the G0W0 approximation on DFT (G0W0@DFT). The optical properties were calculated on top of G0W0@DFT data using the Bethe-Salpeter Equation. We investigate properties from the monomers T and F to tetramers with different sequencing of units TT, TF or FF, always bonded through the usual carbon atoms. As well known for the uniform oligothiophene chains, also here for any TT sequencing we find a torsion angle of $150^{\circ}$, while all other sequencing of units result planar, which can be relevant for film producing. Also we find that the first optical transitions for the oligomers reach a promising threshold of $\sim 3$ eV at the tetramer length, combined with ionization potentials around $\sim 7$ eV, which confirms the relevance of these organic compounds for photovoltaic applications.