Charge-transfer electronic states in organic solar cells: a TDDFT study

The prediction of new organic photovoltaic materials in organic solar cells (OSCs) must include a precise description of charge-transfer states because they are involved in electron-transfer processes such as charge separation and charge recombination which govern the device efficiency. Also, as the experimental performance of an optoelectronic device is measured for nonequilibrium nanostructures, computational approaches need models that can incorporate morphology effects. Usually, this aspect is treated by molecular dynamics simulation (MDS) methodologies; however, methodologies and formalisms to calculate the electron-transfer processes are still controversial and sometimes do not connect their information with the phase morphologies. In this work we propose a simple and fast characterization of electron-transfer processes to find the rate constants by analysing the distribution of vertical excitation energies of both local excitation (LE) and charge-transfer (CT) states using TD-DFT calculations in the donor-acceptor pair structures which were extracted from MDS. This proposal assumes that conformational changes are prevented and equilibria are not achieved while the electron-transfer events take effect, and thus the only pathway that connects the LE and CT states is their surface crossing point where an ideal distribution might exist. Different density functionals and dialectric models were tested. The results indicate a close relationship between the proposal and experimental data for electron-transfer events, suggesting the application of this method in the rational design of new photovoltaic materials.