Assessment of the performance of four dispersion-corrected DFT methods using optoelectronic properties and binding energies of organic monomer/fullerene pairs

Abstract

With the aid of different polymer materials, their properties can be adjusted so as to enhance the efficiencies of heterogeneous organic solar cells. It is known that computational investigations involving density functional theory (DFT) can play an important role in identifying polymers with favourable properties and hence in speeding up the process of designing organic solar cells with higher efficiencies. However, what is often not known is which one of the dispersion-corrected DFT (D-DFT) methods gives the most accurate results (relative to the experimental data) for the various properties of conjugated systems such as are found in heterogeneous organic solar cells. In this study, we employ ωB97x-D, B97-D3, B3LYP-D3, and PBE1PBE-D3 and assess their accuracy by computing binding energies and electronic parameters (such as HOMO and LUMO eigenvalues) of the various (promising) molecular pairings of organic monomers and fullerenes. In addition, we employ time dependent DFT (TD-DFT) to determine optical properties of monomers such as their maximum absorption wavelengths and compare them with the experimental findings. Our results show that B97-D3 and B3LYP-D3 methods give the largest binding energies relative to the other D-DFT methods and they yield (relative to experimental values) the most accurate electronic and absorption results.