  We report theoretical investigations on the role of interfacial bonding
mechanism and its resulting structures to quantum transport in molecular wires.
Two bonding mechanisms for the Au-S bond in an
Au(111)/1,4-benzenedithiol(BDT)/Au(111) junction were identified by ab initio
calculation, confirmed by a recent experiment, which, we showed, critically
control charge conduction. It was found, for Au/ BDT/Au junctions, the hydrogen
atom, bound by a dative bond to the Sulfur, is energetically non-dissociative
after the interface formation. The calculated conductance and junction
breakdown forces of H-non-dissociative Au/BDT/Au devices are consistent with
the experimental values, while the H-dissociated devices, with the interface
governed by typical covalent bonding, give conductance more than an order of
magnitude larger. By examining the scattering states that traverse the
junctions, we have revealed that mechanical and electric properties of a
junction have strong correlation with the bonding configuration. This work
clearly demonstrates that the interfacial details, rather than previously
believed many-body effects, is of vital importance for correctly predicting
equilibrium conductance of molecular junctions; and manifests that the
interfacial contact must be carefully understood for investigating quantum
transport properties of molecular nanoelectronics.
