Electronic transport properties of free-base tape-porphyrin molecular wires studied by self-consistent tight-binding calculations

We investigated by theoretical calculations the electronic states and the transport properties of one of the oligoporphyrin molecular wires, the free-base tape-porphyrins. Inside these molecules the adjacent building blocks, referred to as porphyrin macrocycles, are linked by three conjugating C-C bonds aligned in parallel. We found that the origin of the extremely small highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps of these molecules is the strong coupling between the unoccupied π orbitals of each macrocycle. Then we considered the molecular bridges where these porphyrin molecules are bridged between the aluminum electrodes. We found that the conductances have large values and that the current increases nearly in proportion to the applied bias. These features are explained by the strong hybridization of the HOMO with the electrode wave functions and by the wide bandwidth of the tape porphyrins. Finally we studied the current distribution inside the tape-porphyrin wire. The current is found to flow in an anisotropic way, i.e., it seems to flow along the spatial distribution of the HOMO of the tape porphyrins, reflecting the strong hybridization of the HOMO with the electrode wave functions.