Single working molecule: The controlled cis–trans isomerization (see picture; left cis, right trans isomer) of a single molecule of the azobenzene derivative Disperse Orange 3 on a Au(111) metal surface is acccomplished by injection of tunneling electrons at a certain position (cross in left picture) into the molecule.

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.

Inelastic electron tunneling spectroscopy at low temperatures was used to investigate vibrations of Au(111) and Cu(111). The low-energy peaks at 9 millielectron volts (meV) on Au(111) and 21 meV on Cu(111) are attributed to phonons at surfaces. On Au(111), the phonon energy is not influenced by the different stacking of the surface atoms, but it is considerably influenced by different atomic distances within the surface layer. The spatial variation of the phonon excitation is measured in inelastic electron tunneling maps on Au(111), which display atomic resolution. This atomic resolution is explained in terms of site-specific phonon excitation probabilities.

A scanning tunneling microscope operating at 5 K is used to induce the isomerization of single chloronitrobenzene molecules on Cu(111) and verify the reaction. The threshold voltage of (227+/-7) mV for this reaction is explained based on electron-induced vibrational heating. We propose that the isomerization is initiated by simultaneous excitation of two vibrational molecular modes via inelastically tunneling electrons. This excitation results in a shift of the distribution probability of chlorine and hydrogen positions, which facilitates their mutual exchange.

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.