Determination of energetically preferable Au-S contact atomic structure in stretched single-molecule junctions

Based on the first-principles computations, the nature of the microscopic geometry of the molecule-electrode contacts was addressed. The single-molecule junction was prepared by connecting hexanediothiolate (HDT) to Au(111) electrodes via one, two, and three Au adatoms having coordination number of one (CN1), two (CN2), and, three (CN3), respectively. The contact atomic structure and energy of the stretched Au-HDT-Au junction was observed. The analysis revealed that the contact geometry with lowest coordination number (CN1) is energetically more stable than CN2 and CN3.