Note:The published version in Nature Materials contains an extended manuscript and comprehensive supplementary information. . One of the primary experimental methods to reveal the mechanisms behind electronic transport through metal-molecule interfaces is the study of conductance as a function of molecule length in molecular junctions [4][5][6][7][8][9][10][11][12][13][14] . Previous studies focused on transport governed either by coherent tunneling or hopping, both at low conductance. However, the upper limit of conductance across molecular junctions has not been explored, despite the great potential for efficient information transfer, charge injection and recombination processes at high conductance. Here, we study the conductance properties of highly transmitting metal-molecule-metal interfaces, using a series of single-molecule junctions based on oligoacenes with increasing length. We find that the conductance saturates at an upper limit where it is independent of molecule length. Furthermore, we show that this upper limit can be controlled by the character of the orbital hybridization at the metal-molecule interface. Using two prototype systems, in which the molecules are contacted by either Ag or Pt electrodes, we reveal two different origins for the saturation of conductance. In the case of Ag-based molecular junctions, the conductance saturation is ascribed to a competition between energy level alignment and level broadening, while in the case of Pt-based junctions, the saturation is attributed to a band-like transport. The results are explained by an intuitive model, backed by ab-initio transport calculations. Our findings shed light on the mechanisms that constrain the conductance at the high transmission limit, providing guiding principles for the design of highly conductive metal-molecule interfaces.In order to study the conductance characteristics of highly transmitting molecular junctions, strong electronic coupling is required between the molecule and the electrodes, as well as within the molecule itself 10,11,15,16 . These conditions are achieved in this work by direct hybridization between the π-orbitals of the oligoacene molecules and the frontier orbitals of the metal electrodes, without employing anchoring groups such as thiols that can act as spacers between the orbitals of the molecular backbone and the frontier orbitals of the metal 13,15 . The oligoacenes (Fig. 1a) are linear π-conjugated molecules that can be viewed as short graphene nanoribbons 17 , whose electronic structure is subject to an ongoing research 18 . We study the evolution of conductance as a function of molecule length and compare the conductance characteristics of

Using a break junction technique, we find a clear signature for the formation of conducting hybrid junctions composed of a single organic molecule (benzene, naphthalene, or anthracene) connected to chains of platinum atoms. The hybrid junctions exhibit metallic-like conductance (~0.1-1G0), which is rather insensitive to further elongation by additional atoms. At low bias voltage the hybrid junctions can be elongated significantly beyond the length of the bare atomic chains. Ab initio calculations reveal that benzene based hybrid junctions have a significant binding energy and high structural flexibility that may contribute to the survival of the hybrid junction during the elongation process. The fabrication of hybrid junctions opens the way for combining the different properties of atomic chains and organic molecules to realize a new class of atomic scale interfaces.

We investigate periodical oscillations in the conductance of suspended Au and Pt atomic chains during elongation under mechanical stress. Analysis of conductance and shot noise measurements reveals that the oscillations are mainly related to variations in a specific conduction channel as the chain undergoes transitions between zigzag and linear atomic configurations. The calculated local electronic structure shows that the oscillations originate from varying degrees of hybridization between the atomic orbitals along the chain as a function of the zigzag angle. These variations are highly dependent on the directionality and symmetry of the relevant orbitals, in agreement with the order-of-magnitude difference between the Pt and Au oscillation amplitudes observed in experiment. Our results demonstrate that the sensitivity of conductance to structural variations can be controlled by designing atomic-scale conductors in view of the directional interactions between atomic orbitals

The effect of electron-vibration interaction in atomic-scale junctions with a single conduction channel was widely investigated both theoretically and experimentally. However, the more general case of junctions with several conduction channels has received very little attention. Here we study electron-vibration interaction in multichannel molecular junctions, formed by introduction of either benzene or carbon dioxide between platinum electrodes. By combining shot noise and differential conductance measurements, we analyze the effect of vibration activation on conductance in view of the distribution of conduction channels. Based on the shift of vibration energy while the junction is stretched, we identify vibration modes with transverse and longitudinal symmetry. The detection of different vibration modes is ascribed to efficient vibration coupling to different conduction channels according to symmetry considerations. While most of our observations can be explained in view of the theoretical models for a single conduction channel, the appearance of conductance enhancement, induced by electron-vibration interaction, at high conductance values indicates either unexpected high electron-vibration coupling or interchannel scattering.