Background removal in scanning tunneling spectroscopy of single atoms and molecules on metal surfaces.

Scanning tunneling spectroscopy has developed into a powerful spectroscopic technique that has found wide application in the atomic scale characterization of the electronic properties of clean surfaces as well as adsorbates and defects at surfaces. However, it still lacks the standard methods for data treatment and removal of artifacts in spectra as they are, e.g., common in photoemission spectroscopy. The properties of the atomic scale tip apex--the probe of the instrument--tend to introduce spurious background signals into tunneling spectra. We present and discuss two methods which permit to extract tip-independent information from low temperature tunneling spectra acquired on single atoms and molecules on single crystal surfaces by background subtraction. The methods rely on a characterization of the tip on the clean metal surface. The performance of both methods is demonstrated and compared for simulated and experimental tunneling spectra.

Exchange interaction between single magnetic adatoms.

The magnetic coupling between single Co atoms adsorbed on a copper surface is determined by probing the Kondo resonance using low-temperature scanning tunneling spectroscopy. The Kondo resonance, which is due to magnetic correlation effects between the spin of a magnetic adatom and the conduction electrons of the substrate, is modified in a characteristic way by the coupling of the neighboring adatom spins. Increasing the interatomic distance of a Cobalt dimer from 2.56 to 8.1 A we follow the oscillatory transition from ferromagnetic to antiferromagnetic coupling. Adding a third atom to the antiferromagnetically coupled dimer results in the formation of a collective correlated state.

Kondo effect of molecular complexes at surfaces: ligand control of the local spin coupling.

The spin state of single magnetic atoms and molecules at surfaces is of fundamental interest and may play an important role in future atomic-scale technologies. We demonstrate the ability to tune the coupling between the spin of individual cobalt adatoms with their surroundings by controlled attachment of molecular ligands. The strength of the coupling is determined via the Kondo resonance by low-temperature scanning tunneling spectroscopy. Spatial Kondo resonance mapping is introduced as a novel imaging tool to localize spin centers in magnetic molecules with atomic precision.

Kondo temperature of magnetic impurities at surfaces.

Based on the experimental observation that only the close vicinity of a magnetic impurity at metal surfaces determines its Kondo behavior, we introduce a simple model which explains the Kondo temperatures observed for cobalt adatoms at the (111) and (100) surfaces of Cu, Ag, and Au. Excellent agreement between the model and scanning tunneling spectroscopy experiments is demonstrated. The Kondo temperature is shown to depend on the occupation of the d level determined by the hybridization between the adatom and the substrate with a minimum around single occupancy.

Quantum coherence of image-potential states.

The quantum dynamics of the two-dimensional image-potential states in front of the Cu(100) surface is measured by scanning tunneling microscopy and spectroscopy. The dispersion relation and the momentum resolved phase-relaxation time of the first image-potential state are determined from the quantum interference patterns in the local density of states at step edges. It is demonstrated that the tip-induced Stark shift does not affect the motion of the electrons parallel to the surface.

Surface states of cobalt nanoislands on Cu111.

The electronic structure of thin Co nanoislands on Cu(111) has been investigated below and above the Fermi level (E(F)) by scanning tunneling spectroscopy at low temperature. Two surface related electronic states are found: a strong localized peak 0.31 eV below E(F) and a mainly unoccupied dispersive state, giving rise to quantum interference patterns of standing electron waves on the Co surface. Ab initio calculations reveal that the electronic states are spin polarized, originating from d3(z(2)-r(2))-minority and sp-majority bands, respectively.

Dynamics of high-barrier surface reactions: laser-assisted associative desorption of N2 from Ru(0001)

We have determined the dynamics and energetics of associative desorption of N2 from Ru(0001) using both an experimental technique, laser-assisted associative desorption, and density functional calculations. These show that N2 is preferentially desorbed into very high vibrational states and that the barriers between gas phase N2 and adsorbed N atoms increase from 2 to >3 eV with increasing N coverage on the surface. This experimental technique is found to be quite insensitive to low barrier steps and defects which complicate interpretations from other methods of studying high-barrier surface reactions.