We have studied the structural and electronic properties of tetracyanoethylene (TCNE) molecules on different noble-metal surfaces using scanning tunneling spectroscopy and density functional theory. Striking differences are observed in the TCNE behavior on Au, Ag, and Cu substrates in the submonolayer limit. We explain our findings by a combination of charge-transfer and lattice-matching properties for TCNE across substrates that results in a strong variation of molecule-molecule and molecule-substrate interactions. These results have significant implications for future organic/inorganic nanoscopic devices incorporating molecule-based magnetism.

We have measured the elastic and inelastic tunneling properties of isolated Gd@C(82) molecules on Ag(001) using cryogenic scanning tunneling spectroscopy. We find that the dominant inelastic channel is spatially well localized to a particular region of the molecule. Ab initio pseudopotential density-functional theory calculations indicate that this channel arises from a vibrational cage mode. We further show that the observed inelastic tunneling localization is explained by strong localization in the molecular electron-phonon coupling to this mode.

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We have observed variable negative differential resistance (NDR) in scanning tunneling spectroscopy measurements of a double layer of C 60 molecules on a metallic surface.Minimum to maximum current ratios in the NDR region are tuned by changing the tunneling barrier width. The multi-layer geometry is critical, as NDR is not observed when tunneling into a C 60 monolayer. Using a simple model we show that the observed NDR behavior is explained by voltage-dependent changes in the tunneling barrier height. 2Negative differential resistance (NDR) is a crucial property of several important electronic components [1,2]. Originally observed in highly doped tunneling diodes [3], NDR has been seen in a variety of systems and caused by several different mechanisms [4,5,6,7,8]. Here we present a scanning tunneling spectroscopy (STS) study showing the appearance of NDR in the tunneling signature of thin molecular C 60 films deposited on Au(111). NDR is completely absent for tunneling into a single C 60 monolayer, but emerges when tunneling into second and higher layers of C 60 . In previous STS studies of molecular systems NDR has been commonly attributed to the convolution of energetically localized tip states with the molecular density of states [7]. The NDR observed in our study is inconsistent with this interpretation, but instead stems from the voltage dependence of the tunneling barrier height [4]. We further find that the relative decrease in current, induced by the NDR, increases with increasing tunneling barrier width, allowing for tunability of the NDR behavior. This behavior is explained by using a simple tunneling model. Our experiments were conducted using a homebuilt ultrahigh vacuum (UHV) STM with a PtIr tip. The single-crystal Au(111) substrate was cleaned in UHV and dosed with C 60 using a calibrated Knudsen cell evaporator before being cooled to 7K in the STM stage. dI/dV spectra and images were measured through lock-in detection of the ac tunneling current driven by a 451Hz, 10mV (rms) signal added to the junction bias under open-loop conditions (bias voltage here is defined as the sample potential referenced to the tip). All data were acquired at 7K.Figure 1(a) shows the topographic structure of a single layer of C 60 (monolayer), a second layer of C 60 (bilayer), and a third layer of C 60 (trilayer). Each layer is well ordered 3 and has a topographic structure consistent with previous measurements performed on similar monolayer and layered C 60 systems [9,10]. The step height of each C 60 layer is ~8.0Å.Step edges in the underlying Au(111) substrate lead to 2Å steps that run through the C 60 layers. dI/dV spectra performed on the C 60 monolayer and bilayer are shown in Fig. 1 (b).These spectra exhibit several common features: a shoulder in the filled density of states (V<0) and two peaks in the empty density of states (V>0) that arise from tunneling into the C 60 highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital LUMO, and LUMO+1, respectively [11]. In the monolayer (bilayer) s...