The diversity of electron-transport behaviors of molecular junctions: correlation with the electron-transport pathway

We report the electron-transport behaviors of a number of molecular junctions composed of pi-conjugated molecular wires. From calculations performed by using density functional theory (DFT) combined with the non-equilibrium Green's function (NEGF) method, we found that the length-conductivity relations are diverse, depending on the particular molecular structures. The results reveal that the conductance-length dependence follows an exponential law for many conjugated molecules with a single channel, such as oligothiophene, oligopyrrole and oligophenylene. Therefore, a quantitative relation between the energy gap (E(g))(infinity) of the molecular wire and the attenuation factor beta can be defined. However, when the molecular wires have multichannels, the decay of conductance does not follow the exponential relation. For example, the conductance of porphyrin-based oligomers and fused thiophene decays almost linearly. The diversity of electron-transport behaviors of molecular junctions is directly dominated by the electron-transport pathway.