Abstract
Fermi's golden rule, a remarkable concept for the transition probability involving continuous states, is applicable to the interfacial electron-transporting efficiency via correlation with the surface density of states (SDOS). Yet, this concept has not been reported to tailor single-molecule junctions where gold is an overwhelmingly popular electrode material due to its superior amenability in regenerating molecular junctions. At the Fermi level, however, the SDOS of gold is small due to its fully filled d-shell. To increase the electron-transport efficiency, herein, gold electrodes are modified by a monolayer of platinum or palladium that bears partially filled d-shells and exhibits significant SDOS at the Fermi energy. An increase by 2-30 fold is found for single-molecule conductance of α,ω-hexanes bridged via common headgroups. The improved junction conductance is attributed to the electrode self-energy which involves a stronger coupling with the molecule and a larger SDOS participated by d-electrons at the electrode-molecule interfaces.
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