Geometric Effects on Conductance in Single Molecule Electron Transport Junctions

We studied electron transport properties of a dithiol‐benzene molecule covalently bonded between two gold electrodes by combining ab initio calculations for the central molecule and a green function method to calculate electron transport. Due to the large computational demand, this type of calculations usually involves certain ways of simplification. The simplification commonly used is to fix the contact surface of the electrodes by ignoring the disturbance of the Au contact surface by contacting with the central molecule, i.e. without scattering region relaxation. In this study, we intended to resolve the difference between models with and without the above simplification. The large conductance found in our models without scattering region relaxation is due to the highly symmetric arrangement of the Au contact surface and those layers near the contact. The disturbance of the Au contact surface by the contact of the central molecule is important since the increase of the Au‐S bond and the distortion of the Au atom on the FCC site can lower the transmission coefficient between the two electrodes. In order to obtain better results, the model should include scattering region relaxation. However, when such relaxation is not applicable or demands too much calculation resource, the center molecule of the electronic transport junction should be at least optimized by the calculation level including electronic correlation, i.e. post‐HF methods.