Temperature calibration for diffusion experiments to sub-Kelvin precision.

Arrhenius plots are often used to determine energy barriers and prefactors of thermally activated processes. The precision of thus determined values depends crucially on the precision of the temperature measurement at the sample surface. We line out a procedure to determine the absolute temperature of a metal sample in a cryogenic scanning tunneling microscope between 5 K and 50 K with sub-Kelvin precision. We demonstrate the dependence of prefactor and diffusion energy on this calibration for diffusion of CO on Cu(111) and on Ag(100) measured in the temperature range from 30 K to 38 K and 19 K to 23 K, respectively.

Imaging the Bonds of Dehalogenated Benzene Radicals on Cu(111) and Au(111).

Dissociative adsorption of doubly substituted benzene molecules leads to formation of benzyne radicals. In this study, co-adsorbed hydrogen molecules are used in scanning tunneling hydrogen microscopy to enhance the contrast of the meta- and the para-isomers of these radicals on Cu(111) and Au(111). Up to three hydrogen molecules are attached to one radical. One hydrogen molecule reveals the orientation of the carbon ring and its adsorption site, allowing discrimination between the two radicals. Two hydrogen molecules reflect the bond picture of the carbon skeleton and reveals that adsorption on Cu(111) distorts the meta- isomer differently from its gas-phase distortion. Three hydrogen molecules allow us to determine the bond picture of a minor species.

Physisorption versus chemisorption of oxygen molecules on Ag(100).

We compare the adsorption of oxygen molecules on Ag(100) at 60 K and at 100 K. At both temperatures, the molecules form islands. Differences between the species adsorbed at the two temperatures in both low-temperature scanning tunneling microscopy and inelastic electron tunneling spectroscopy are attributed to two different adsorption states, a chemisorbed state after 100 K adsorption and a physisorbed state after 60 K adsorption.

A switch based on self-assembled thymine.

The DNA base thymine is deposited at 100 K on Cu(111) and investigated and manipulated by low-temperature scanning tunneling microscopy at 5 K. At submonolayer coverage paired rows are observed. At monolayer coverage a hexagonal commensurate self-assembled layer with the methyl group pointing away from the surface forms. A reversible local manipulation of molecules within the self-assembled layer is demonstrated. This manipulation is interpreted as an out-of-plane relaxation of molecules within the layer induced by the change of the adsorption geometry of individual molecules between two meta-stable orientations. A positive field of 2-4 V leads to this local change in the molecular arrangement, while a field larger than 4 V restores the original geometry.

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.

Dissociation of oxygen on Ag(100) induced by inelastic electron tunneling.

Scanning tunneling microscopy (STM) is used to study the dissociation of molecular oxygen on Ag(100) induced by inelastic electron tunneling (IET) at 5 K. This dissociation is possible above 3.3 V with a yield of (3.63 ± 0.47) × 10(-9) per electron. Dissociation leads to three different types of hot atom motion: lateral motion, a cannon ball mechanism, and abstractive dissociation. Analysis of the I-t characteristics during dissociation suggests that the dissociation is proceeded by an adsorption site change.

Local investigation of femtosecond laser induced dynamics of water nanoclusters on Cu(111).

We explore the dynamics of low temperature interfacial water nanoclusters on Cu(111) by femtosecond-laser excitation, scanning tunneling microscopy and density functional theory. Laser illumination is used to induce single molecules to diffuse within water clusters and across the surface, breaking and reforming hydrogen bonds. A linear diffusion probability with laser fluence is observed up to 0.6 J/m2 and we suggest that diffusion is initiated by hot electron attachment and detachment processes. The density functional calculations shed light on the detailed molecular mechanism for water diffusion that is determined by the local structure of the water clusters.

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.

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.

Faceting during the transformation of amorphous to crystalline ice.

We study the thermally activated transition from amorphous to crystalline ice (D2O) on Cu(111) with high-resolution scanning tunneling microscopy. Annealing of amorphous solid water up to the desorption temperature of 149 K results subsequently in monomer decorated double bilayers with different superstructure, a faceted surface, pyramidal islands, and nanocrystallites of distinct height at different coverages. Though all structures are truncations from crystalline water ice, for none of them is the ice bilayer found to be the terminating surface.