Real-space imaging of inelastic Friedel-like surface oscillations emerging from molecular adsorbates.

We report real space imaging measurements of inelastic Friedel oscillations. The inelastic electron tunneling spectroscopy, using scanning tunneling microscopy, around dimers of dichlorobenze adsorbates on Au(111) surface display clear spatial modulations that we attribute to inelastic scattering at the molecular sites caused by molecular vibrations. Due to local interactions between the adsorbate and the surface states, the molecular vibrations generate a redistribution of the charge density at energies in a narrow range around the inelastic mode. Our experimental findings are supported by theoretical arguments.

Diffusion and dimer formation of CO molecules induced by femtosecond laser pulses.

We investigate two fundamental steps of a nonadiabatic surface process, the photo-induced movement and approach of CO molecules on the Cu(111) surface, at a hitherto unachieved single-molecule level through scanning tunneling microscope imaging. For the close approach of two CO molecules, we not only determine the nonadiabatic diffusion barrier (87 meV), but also discover a femto-second-laser-induced transient attraction (30 meV) of the usually repelling CO molecules.

Hard repulsive barrier in hot adatom motion during dissociative adsorption of oxygen on Ag(100).

Random pairing simulation and low temperature scanning tunneling microscopy (STM) are used to investigate the detailed O(2) dissociative adsorption processes at 200 K for various coverages. The distribution of oxygen adatoms shows a strong repulsion between the adsorbates with a radius of approximately 0.8 nm. The comparison between STM results and simulation reveals two prominent pairing distances of 2 and 4 nm and their branching ratio is about 2:1. These findings shed new light on the origin of the large intrapair distances found and on the process behind the empirical "eight-site rule."

Electron damage to supported ice investigated by scanning tunneling microscopy and spectroscopy.

We study the interaction of low-energy electrons with crystalline ice (D2O) on Cu(111) by low-temperature scanning tunneling microscopy and spectroscopy. Electrons induce dissociation of the molecules with a threshold of approximately 3 eV. The large dissociation yield of the order of 10(-8)/electron and the extended area of dissociation are attributed to a shift in conduction band during the dissociation. Voltage dependent differences in imaging of ice and dissociated ice are reflected in the spectroscopic signature.

Manipulation and control of hydrogen bond dynamics in absorbed ice nanoclusters.

Inelastic electron tunneling is used to explore the dynamics of ice nanoclusters adsorbed on Ag(111). The diffusion of entire nanoclusters or internal hydrogen bond rearrangement can be selectively controlled by injecting electrons either directly into the clusters themselves or indirectly ("indirect inelastic electron tunneling") into the substrate at distances of up to 20 nm from them; a reaction probability that oscillates with the tip-cluster lateral distance presents evidence that surface state electrons mediate the excitation. Density functional theory calculations reveal a strong sensitivity of the computed activation energies of the individual processes to the applied electrical field.

An instrument to investigate femtochemistry on metal surfaces in real space.

A newly established combination of a femtosecond laser with a low temperature scanning tunneling microscope is described, which facilitates one to analyze femtochemistry on metal surfaces in real space. The combined instrument enables focusing the laser to some tens of micrometers and guiding it reproducibly into the tunneling gap with the aid of in situ movable mirrors. Furthermore, a method to determine the focus size on the sample is presented. The focus size is used to calculate the electron and phonon temperatures at the surface. Despite the additional noise introduced by laser operation the vertical resolution of the microscope lies below 1 pm. The potential of the instrument is demonstrated on para-chloronitrobenzene clusters adsorbed on Au(111). Single chloronitrobenzene molecules diffuse upon femtosecond laser irradiation; some smaller clusters rotate by multiples of 30 degrees ; clusters of less compact form rearrange to close-packed clusters.