First-Principles Study of Electrochemical Gate-Controlled Conductance in Molecular Junctions

A first-principles computational method is developed to study the electrochemical gate-controlled conductance in molecular junctions. It has been applied to a single molecular field-effect transistor made by a perylene tetracaboxylic diimide molecule connected to gold electrodes and has successfully reproduced the experimentally observed huge gate voltage effect on the current. It is found that such a significant gain is a result of the large polarization of the molecule induced by the huge local electrical field generated by the electrochemical gate. The resonant electron tunneling through unoccupied molecular orbitals is shown to be the dominant transport process.