Temperature effects on the transport properties of molecules.

Recent experiments found an unusual temperature-induced large shift in the resonant-tunneling voltage of certain molecules. We report first-principles calculations showing that such behavior can be caused by the excitation of rotational modes of ligands. These modes have classical characteristics, i.e., the maximum excursion is dominant, while at the same time they have a significant effect on the energy levels responsible for resonant tunneling. The proposed mechanism of ligand rotations is unique to molecules and accounts for the fact that the effect is not seen in semiconductor nanostructures.