Forces and currents in carbon nanostructures: are we imaging atoms?

First-principles calculations show that the rich variety of image patterns found in carbon nanostructures with the atomic force and scanning tunneling microscopes can be rationalized in terms of the chemical reactivity of the tip and the distance range explored in the experiments. For weakly reactive tips, the Pauli repulsion dominates the atomic contrast and force maxima are expected on low electronic density positions as the hollow site. With reactive tips, the interaction is strong enough to change locally the hybridization of the carbon atoms, making it possible to observe atomic resolution in both the attractive and the repulsive regime although with inverted contrast. Regarding STM images, we show that in the near-contact regime, due to current saturation, bright spots correspond to hollow positions instead of atomic sites, providing an explanation for the most common hexagonal pattern found in the experiments.

Theoretical study of electronic and transport properties of PPy-Pt(111) and PPy-C(111):H interfaces.

We present a first-principles study of promising hybrid organic-inorganic interface systems consisting of a polypyrrole (PPy) chain sandwiched between metallic Pt(111) or hydrogen-terminated diamond C(111):H electrodes. We combine ab initio density-functional-theory total energy calculations, Green's function approach and the complex band-structure method in order to determine electronic and transport properties of those organic-semiconductor/metal (semiconductor) interfaces. We analyze one- and multi-bond nanocontact formation including structural modification (H desorption) as well as PPy length dependence. For selected ground state configurations of the considered interface systems we study their energetics and structural properties. Through the analysis of the local density of states, in particular isosurfaces of the charge density, the mechanism of the charge transfer and the charge neutrality levels are determined. The voltage dependence of the electrical conductance and the I-V characteristics are compared to the transport properties based on the complex band-structure method. The obtained results support recent experiments, where PPy nanowires are formed via electrochemical synthesis and placed between platinum or diamond microelectrodes.