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Understanding the properties of electronic transport across metal-molecule interfaces is of central importance for controlling a large variety of molecular-based devices such as organic light emitting diodes, nanoscale organic spin-valves and single-molecule switches. 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. Previous studies focused on transport governed either by 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. 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., Comment: 11 pages, 5 figures, Supplementary Information

We report a combined experimental and theoretical study of the Kondo effect in a series of binuclear metal-organic complexes of the form [(Me(hfacac)_2)_2(bpym)]^0, with Me = Nickel (II), Manganese(II), Zinc (II); hfacac = hexafluoroacetylacetonate, and bpym = bipyrimidine, adsorbed on Cu(100) surface. While Kondo-features did not appear in the scanning tunneling spectroscopy spectra of non-magnetic Zn_2, a zero bias resonance was resolved in magnetic Mn_2 and Ni_2 complexes. The case of Ni_2 is particularly interesting as the experiments indicate two adsorption geometries with very different properties. For Ni_2-complexes we have employed density functional theory to further elucidate the situation. Our simulations show that one geometry with relatively large Kondo temperatures T_K ~ 10K can be attributed to distorted Ni_2 complexes, which are chemically bound to the surface via the bipyrimidine unit. The second geometry, we assign to molecular fragmentation: we suggest that the original binuclear molecule decomposes into two pieces, including Ni(hexafluoroacetylacetonate)_2, when brought into contact with the Cu-substrate. For both geometries our calculations support a picture of the (S=1)-type Kondo effect emerging due to open 3d shells of the individual Ni^{2+} ions., Comment: 11 pages, 10 figures, Supplementary Information is attached as a separate PDF file, submitted to Phys. Rev. B

We present a systematic investigation of molecule-metal interactions for transition-metal phthalocyanines (TMPc, with TM = Fe, Co, Ni, Cu) adsorbed on Ag(100). Scanning tunneling spectroscopy and density functional theory provide insight into the charge transfer and hybridization mechanisms of TMPc as a function of increasing occupancy of the 3d metal states. We show that all four TMPc receive approximately one electron from the substrate. Charge transfer occurs from the substrate to the molecules, inducing a charge reorganization in FePc and CoPc, while adding one electron to ligand \pi-orbitals in NiPc and CuPc. This has opposite consequences on the molecular magnetic moment: in FePc and CoPc the interaction with the substrate tends to reduce the TM spin, whereas in NiPc and CuPc an additional spin is induced on the aromatic Pc ligand, leaving the TM spin unperturbed. In CuPc, the presence of both TM and ligand spins leads to a triplet ground state arising from intramolecular exchange coupling between d and \pi electrons. In FePc and CoPc the magnetic moment of C and N atoms is antiparallel to that of the TM. The different character and symmetry of the frontier orbitals in the TMPc series leads to varying degrees of hybridization and correlation effects, ranging from the mixed-valence (FePc, CoPc) to the Kondo regime (NiPc, CuPc). Coherent coupling between Kondo and inelastic excitations induces finite-bias Kondo resonances involving vibrational transitions in both NiPc and CuPc and triplet-singlet transitions in CuPc., Comment: 14 pages, 11 figures