The electronic and transport properties of a molecular junction studied by an integrated piecewise thermal equilibrium approach

An integrated piecewise thermal equilibrium approach based on the first-principles calculation method has been developed to calculate bias dependent electronic structures and current- and differential conductance-voltage characteristics of the gold-benzene-1,4-dithiol-gold molecular junction. The calculated currents and differential conductance have the same order of magnitude as experimental ones. An electron transfer was found between the two electrodes when a bias is applied, which renders the two electrodes to have different local electronic structures. It was also found that when Au 5 d electrons were treated as core electrons the calculated currents were overestimated, which can be understood as an underestimate of the Au-S covalent bonding and consequently the contact potential barrier and the replacement of delocalized Au 5 d carriers by more itinerant delocalized Au 6 s p carriers in the electrodes.