Nonclassical Optical Properties of Mesoscopic Gold.

Gold nanostructures have important applications in nanoelectronics, nano-optics, and in precision metrology due to their intriguing optoelectronic properties. These properties are governed by the bulk band structure but to some extent are tunable via geometrical resonances. Here we show that the band structure of gold itself exhibits significant size-dependent changes already for mesoscopic critical dimensions below 30 nm. To suppress the effects of geometrical resonances and grain boundaries, we prepared atomically flat ultrathin films of various thicknesses by utilizing large chemically grown single-crystalline gold platelets. We experimentally probe thickness-dependent changes of the band structure by means of two-photon photoluminescence and observe a surprising 100-fold increase of the nonlinear signal when the gold film thickness is reduced below 30 nm allowing us to optically resolve single-unit-cell steps. The effect is well explained by density functional calculations of the thickness-dependent 2D band structure of gold.

Spin Control Induced by Molecular Charging in a Transport Junction.

The ability of molecules to maintain magnetic multistability in nanoscale-junctions will determine their role in downsizing spintronic devices. While spin-injection from ferromagnetic leads gives rise to magnetoresistance in metallic nanocontacts, nonmagnetic leads probing the magnetic states of the junction itself have been considered as an alternative. Extending this experimental approach to molecular junctions, which are sensitive to chemical parameters, we demonstrate that the electron affinity of a molecule decisively influences its spin transport. We use a scanning tunneling microscope to trap a meso-substituted iron porphyrin, putting the iron center in an environment that provides control of its charge and spin states. A large electron affinity of peripheral ligands is shown to enable switching of the molecular S = 1 ground state found at low electron density to S = 1/2 at high density, while lower affinity keeps the molecule inactive to spin-state transition. These results pave the way for spin control using chemical design and electrical means.

Shifting the Voltage Drop in Electron Transport Through a Single Molecule.

A Mn-porphyrin was contacted on Au(111) in a low-temperature scanning tunneling microscope (STM). Differential conductance spectra show a zero-bias resonance that is due to an underscreened Kondo effect according to many-body calculations. When the Mn center is contacted by the STM tip, the spectrum appears to invert along the voltage axis. A drastic change in the electrostatic potential of the molecule involving a small geometric relaxation is found to cause this observation.

Relevance of hybridization and filling of 3d orbitals for the Kondo effect in transition metal phthalocyanines.

Magnetic organic molecules, such as 3d transition metal phthalocyanines (TMPc), exhibit properties which make them promising candidates for future applications in magnetic data storage or spin-based data processing. Due to their small size, however, TMPc molecules are prone to quantum effects. For example, the interaction of uncompensated molecular spins with conduction electrons of the substrate may lead to the formation of a many-body singlet state, which gives rise to the so-called Kondo effect. Although the Kondo effect of TMPc molecules has been the object of several investigations, a consistent picture to describe under which conditions a Kondo state is formed is still missing. Here, we study the Kondo properties of MnPc on Ag(001) by means of the low-temperature scanning tunneling spectroscopy (LT-STS) measurements. Differential conductance dI/dU spectra reveal a zero-bias peak that is localized on the Mn ion site. Ab initio calculations combined with a many-body treatment of the multiorbital interaction show that the local Hund coupling favors the high-spin configuration on the 3d shell of the central TM atom. Therefore, each orbital gets close to its individual half-filling creating the necessary condition for many of the 3d orbitals to contribute to the observed Kondo resonance. This, however, happens only for the 3dz(2) orbital, whose hybridization to the substrate is much stronger than for the other orbitals thanks to its shape and its orientation.