Microscopic theory of single-electron tunneling through molecular-assembled metallic nanoparticles

We present a microscopic theory of single-electron tunneling through metallic nanoparticles connected to the electrodes through molecular bridges. It combines the theory of electron transport through molecular junctions with the description of the charging dynamics on the nanoparticles. We apply the theory to study single-electron tunneling through a gold nanoparticle connected to the gold electrodes through two representative benzene-based molecules. We calculate the background charge on the nanoparticle induced by the charge transfer between the nanoparticle and linker molecules, the capacitance and resistance of molecular junction using a first-principles based nonequilibrium Green’s-function theory. We demonstrate the variety of transport characteristics that can be achieved through “engineering” of the metal-molecule interaction.