The characteristics of molecular electronic devices are critically determined by metal-organic interfaces, which influence the arrangement of the orbital levels that participate in charge transport.Studies on self-assembled monolayers (SAMs) show (molecule-dependent) level shifts as well as transport-gap renormalization, suggesting that polarization effects in the metal substrate play a key role in the level alignment with respect to the metal's Fermi energy. Here, we provide direct evidence for an electrode-induced gap renormalization in single-molecule junctions. We study charge transport in single porphyrin-type molecules using electrically gateable break junctions.In this set-up, the position of the occupied and unoccupied levels can be followed in situ and with simultaneous mechanical control. When increasing the electrode separation, we observe a substantial increase in the transport gap with level shifts as high as several hundreds of meV for displacements of a fewÅngstroms. Analysis of this large and tunable gap renormalization with image-charge calculations based on atomic charges obtained from density functional theory confirms and clarifies the dominant role of image-charge effects in single-molecule junctions.

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Molecular electronics aims at exploiting the internal structure and electronic orbitals of molecules to construct functional building blocks. To date, however, the overwhelming majority of experimentally realized single-molecule junctions can be described as single quantum dots, where transport is mainly determined by the alignment of the molecular orbital levels with respect to the Fermi energies of the electrodes and the electronic coupling with those electrodes. Particularly appealing exceptions include molecules in which two moieties are twisted with respect to each other and molecules in which quantum interference effects are possible. Here, we report the experimental observation of pronounced negative differential conductance in the current-voltage characteristics of a single molecule in break junctions. The molecule of interest consists of two conjugated arms, connected by a non-conjugated segment, resulting in two coupled sites. A voltage applied across the molecule pulls the energy of the sites apart, suppressing resonant transport through the molecule and causing the current to decrease. A generic theoretical model based on a two-site molecular orbital structure captures the experimental findings well, as confirmed by density functional theory with non-equilibrium Green's functions calculations that include the effect of the bias. Our results point towards a conductance mechanism mediated by the intrinsic molecular orbitals alignment of the molecule.

We have studied the gate and temperature dependence of molecular junctions containing sulfur end-functionalized tercyclohexylidenes. At low temperatures we find temperature-independent transport; at temperatures above 150 K the current increases exponentially with increasing temperature. Over the entire temperature range (10−300 K), and for different gate voltages, a simple toy model of transport through a single level describes the experimental results. In the model, the temperature dependence arises from the Fermi distribution in the leads and in a three-parameter fit we extract the level position and the tunnel rates at the left and right contact. We find that these parameters increase as the bias voltage increases.