The effect of fluctuations, thermal and otherwise, on the temperature dependence of thermopower in aromatic chain single-molecule junctions

We report a theoretical study of the thermopower of single-molecule junctions with focus on phenyl-based molecular junctions. In contrast to prior studies, thermal fluctuations of the torsional angle between the phenyl rings and variations in the position of the molecular level alignment with respect to the electrode Fermi energy were taken into account. Full thermopower histograms were obtained, and their dependence on the magnitude of the fluctuations was studied. We found that at large molecular orbital variations, the thermopower becomes strongly dependent on the torsion angle and can even change sign. This results in a marked effect of fluctuations on the thermopower distribution, yielding an average thermopower at high temperatures that differs (smaller or larger) from the fluctuation-free value, depending on the strength of fluctuations. We therefore conclude that fluctuations should be taken into account both when extracting single-molecule parameters, such as the molecular level-Fermi level offset, and in predictions of the thermopower of molecular junctions.