DFT and TD-DFT Calculations of Orbital Energies and Photovoltaic Properties of Small Molecule Donor and Acceptor Materials Used in Organic Solar Cells

DFT and TD-DFT calculations of HOMO and LUMO energies and photovoltaic properties are carried out on four selected pentathiophene donor and one IDIC-4F acceptor molecules using B3LYP and PBE0 functionals for the ground state energy calculations and CAM-B3LYP functional for the excited state calculations. The discrepancy between the calculated and experimental energies is reduced by correlating them with a linear fit. The fitted energies of HOMO and LUMO are used to calculate the Voc of an OSC based on these donors and acceptor blend and compared with experimental values. Using the Scharber model the calculated PCE of the donor-acceptor molecules agree with the experiment. It has been found that fluorine substitution can be used to improve charge transport by reducing the electron and hole reorganization energies of the molecules. It is also found that the introduction of fluorine onto the donor pentathiophene unit of the donor molecule results in a change of polarity of the distributed charges in the molecule due to the high electronegativity of the fluorine atom. The quantum chemical potential (μ), chemical hardness (η) and electronegativity (χ), and electrostatic potential maps (EPMs) are also calculated to identify different charge distribution regions in all five molecules.