Electronic and carrier transport properties of small molecule donors

As electron donor/acceptor materials for organic photovoltaic cells, small-molecules donors/acceptor are attracting more and more attention. In this work, we investigated the electronic structures, electrochemical properties, and charge carrier transport properties of four recently-synthesized small-molecule donors/acceptor, namely, DPDCPB (A), DPDCTB (B), DTDCPB (A1), and DTDCTB (B1), by a series of ab initio calculations. The calculations look into the electronic structure of singly oxidized and reduced molecules, the first anodic and cathodic potentials, and the electrochemical gaps. Results of our calculations were in accord with those from experiments. Using Marcus theory, we also computed the reorganization energies of hole/electron hoppings, as well as hole/electron transfer integrals of multiple possible molecular dimer configurations. Our calculations indicated that the electron/hole transport properties are very sensitive to the relative separations/orientations between neighboring molecules. Due to high reorganization energies for electron hopping, the hole mobilities in the molecular crystals are at least an order of magnitude higher than the electron mobilities.