A Computational Study of the Electronic Energy and Charge Transfer Rates and Pathways in the Tetraphenyldibenzoperiflanthene/Fullerene Interfacial Dyad.

The electronic transition rates and pathways underlying interfacial charge separation in tetraphenyldibenzoperiflanthene:fullerene (DBP:C) blends are investigated computationally. The analysis is based on a polarization-consistent framework employing screened range-separated hybrid functional in a polarizable continuum model to parametrize Fermi's golden rule rate theory. The model considers the possible transitions within the 25 lowest excited states of a DBP:C dyad that are accessible by photoexcitation. The different identified pathways contributing to charge carrier generation include electron and hole transfer and backtransfer, exciton transfer, and internal relaxation steps. The larger density of states of C appears to explain the previously observed larger efficiency for charge separation through hole transfer mechanism. We also analyze the validity of the high-temperature and short-time semiclassical approximations of the FGR theory, where both overestimated and underestimated Marcus theory based constants can be affected.