"Oh yes, oh yes, these are the atoms!" A personal recollection from the times of the invention of the STM.

The scanning tunneling microscope, invented and developed in the 1980s in the IBM research laboratory in Rüschlikon, has become the dominent scientific tool in surface science and together with its younger brother the atomic force microscope, is widely used also in many other modern research areas. This account contains very personal anecdotal memories from a colleague who worked in a neighboring lab in Rüschlikon describing some events at the periphery of the development of this ingenious instrument.

Single-molecule chemistry and analysis: mode-specific dehydrogenation of adsorbed propene by inelastic electron tunneling.

A single propene molecule, located in the junction between the tip of a scanning tunneling microscope (STM) and a Cu(211) surface can be dehydrogenated by inelastic electron tunneling. This reaction requires excitation of the asymmetric C-H stretching vibration of the ═CH(2) group. The product is then identified by inelastic electron tunneling action spectroscopy (IETAS).

Switching the chirality of single adsorbate complexes.

Pumped up: Propene molecules form chiral complexes when adsorbed on a copper surface. Inelastically scattered tunneling electrons from the tip of a scanning tunneling microscope induce rotation or diffusion of the adsorbate on the surface. Higher tunneling currents can lead to conversion of the adsorbate into the opposite enantiomer.

Molecular aggregation within self-ordered monolayers.

The monolayer growth of pyrimido-pentaphenylbenzene (NPB) on Cu(111) is investigated by means of low-temperature scanning tunneling microscopy (LT-STM). The pyrimidine side group gives rise to a pronounced resonant tunneling state and, furthermore, affects molecular self-ordering. Different molecular aggregates are formed inside the hexagonal closed packed monolayer. A structure model for the monolayer is proposed and the temperature dependence of this self-ordering process is investigated by varying the preparation temperature between 270 and 370 K. The intermolecular bonding of the aggregates is demonstrated by STM manipulation experiments. Moreover, different aggregations of the molecules induce characteristic energy shifts in the resonant tunneling state, as revealed by means of scanning tunneling spectroscopy.

A rack-and-pinion device at the molecular scale.

Molecular machines, and in particular molecular motors with synthetic molecular structures and fuelled by external light, voltage or chemical conversions, have recently been reported. Most of these experiments are carried out in solution with a large ensemble of molecules and without access to one molecule at a time, a key point for future use of single molecular machines with an atomic scale precision. Therefore, to experiment on a single molecule-machine, this molecule has to be adsorbed on a surface, imaged and manipulated with the tip of a scanning tunnelling microscope (STM). A few experiments of this type have described molecular mechanisms in which a rotational movement of a single molecule is involved. However, until now, only uncontrolled rotations or indirect signatures of a rotation have been reported. In this work, we present a molecular rack-and-pinion device for which an STM tip drives a single pinion molecule at low temperature. The pinion is a 1.8-nm-diameter molecule functioning as a six-toothed wheel interlocked at the edge of a self-assembled molecular island acting as a rack. We monitor the rotation of the pinion molecule tooth by tooth along the rack by a chemical tag attached to one of its cogs.

Exploring the interatomic forces between tip and single molecules during STM manipulation.

The interaction between a single molecule and the STM tip during intramolecular manipulation is investigated in detail. We show that the conformational change of complex organic molecules can be induced reversibly and very reliably by using exclusively attractive forces. By studying the dependence of this process on the bias voltage and the tip position, the driving forces are characterized. Different regimes of tip-molecule interactions are observed as a function of the distance.

Electric field-induced isomerization of azobenzene by STM.

The electric field applied between the tip of a scanning tunneling microscope and a metallic surface is shown to induce the reversible trans-cis isomerization of single azobenzene derivatives adsorbed on a Au(111) surface. The investigated molecule is symmetrically equipped with four tert-butyl groups, which decouple the azobenzene core from the metallic surface, facilitating the formation of highly ordered islands. Due to the spatial extension of the electric field, it is possible to switch many molecules within the same island simultaneously.

Trapping and moving metal atoms with a six-leg molecule.

Putting to work a molecule able to collect and carry adatoms in a controlled way on a surface is a solution for fabricating atomic structures atom by atom. Investigations have shown that the interaction of an organic molecule with the surface of a metal can induce surface reconstruction down to the atomic scale. In this way, well-defined nanostructures such as chains of adatoms, atomic trenches and metal-ligand compounds have been formed. Moreover, the progress in manipulation techniques induced by a scanning tunnelling microscope (STM) has opened up the possibility of studying artificially built molecular-metal atomic scale structures, and allowed the atom-by-atom doping of a single C(60) molecule by picking up K atoms. The present work goes a step further and combines STM manipulation techniques with the ability of a molecule to assemble an atomic nanostructure. We present a well-designed six-leg single hexa-t-butyl-hexaphenylbenzene (HB-HPB) molecule, which collects and carries up to six copper adatoms on a Cu(111) surface when manipulated with a STM tip. The 'HB-HPB-Cu atoms' complex can be further manipulated, bringing its Cu freight to a predetermined position on the surface where the metal atoms can finally be released.

Controlling the electronic interaction between a molecular wire and its atomic scale contacting pad.

We report a quantitative study on the electronic interaction between a molecular wire and its atomic scale metallic contacting pad. A so-called "reactive Lander" molecule is manipulated using a low-temperature scanning tunneling microscope to form a planar one-end electronic contact. The increase of the STM contrast at the junction location is discussed by means of the electronic interaction between the contacting group of the molecular wire and the end atoms of the nanopad.

Controlled low-temperature molecular manipulation of sexiphenyl molecules on Ag111 using scanning tunneling microscopy.

A novel scanning tunneling microscope manipulation scheme for a controlled molecular transport of weakly adsorbed molecules is demonstrated. Single sexiphenyl molecules adsorbed on a Ag(111) surface at 6 K are shot towards single silver atoms by excitation with the tip. To achieve atomically straight shooting paths, an electron resonator consisting of linear standing-wave fronts is constructed. The sexiphenyl manipulation signals reveal a pi ring flipping as the molecule moves from the hcp to fcc site. Ab initio calculations show an incorporation of the Ag atom below the center of a pi ring.

Direct imaging of Cu dimer formation, motion, and interaction with Cu atoms on Ag(111).

We have investigated the formation and motion of copper adatoms and addimers on Ag(111) between 6 and 25 K with low-temperature scanning tunneling microscopy. The presence of atoms and dimers alters the motion of atoms and dimers via the long-range interaction mediated by the electrons in the two-dimensional surface state band. Above 16 K, dimers show quantum rotor behavior with altered rotational behavior in the presence of an additional adatom. The most favorable diffusional motion of the dimer is identified in combination with molecular dynamics calculations to be a zigzag out-of-cell motion starting above 24 K.

Scattering of surface state electrons at large organic molecules.

The scattering of surface state electrons at Lander-type molecules on Cu(111) is investigated by means of scanning tunneling microscope (STM) experiments at low temperature and model calculations. Specific information concerning the electronic interaction of the different internal groups of the molecule with the surface is obtained. Remarkably, the central molecular wire of the molecule, although decoupled from the surface by spacer groups and therefore not visible in STM images, is the main one responsible for scattering of surface state electrons.

The scanning tunnelling microscope as an operative tool: doing physics and chemistry with single atoms and molecules.

The scanning tunnelling microscope, initially invented to image surfaces down to the atomic scale, has been further developed in the last few years to an operative tool, with which atoms and molecules can be manipulated at will at low substrate temperatures in different manners to create and investigate artificial structures, whose properties can be investigated employing spectroscopic dI/dV measurements. The tunnelling current can be used to selectively break chemical bonds, but also to induce chemical association. These possibilities give rise to startling new opportunities for physical and chemical experiments on the single atom and single molecule level. Here we provide a short overview on recent results obtained with these techniques.

Snell's law for surface electrons: refraction of an electron gas imaged in real space.

On NaCl(100)/Cu(111) an interface state band is observed that descends from the surface-state band of the clean copper surface. This band exhibits a Moiré-pattern-induced one-dimensional band gap, which is accompanied by strong standing-wave patterns, as revealed in low-temperature scanning tunneling microscopy images. At NaCl island step edges, one can directly see the refraction of these standing waves, which obey Snell's refraction law.

Site determination and thermally assisted tunneling in homogenous nucleation.

A combined low-temperature scanning tunneling microscopy and density functional theory study on the binding and diffusion of copper monomers, dimers, and trimers adsorbed on Cu(111) is presented. Whereas atoms in trimers are found in fcc sites only, monomers as well as atoms in dimers can occupy the fcc as well as the metastable hcp site. In fact the dimer fcc-hcp configuration is only 1.3 meV less favorable with respect to the fcc-fcc configuration. This enables a confined intracell dimer motion, which at temperatures below 5 K is dominated by thermally assisted tunneling.

Probing the different stages in contacting a single molecular wire.

A crucial problem in molecular electronics is the control of the electronic contact between a molecule and its electrodes. As a model system, we investigated the contact between the molecular wire group of a C90H98 (Lander) molecule and the edge of a Cu(111) monatomic step. The reproducible contact and decontact of the wire was obtained by manipulating the Lander with a low temperature scanning tunneling microscope. The electronic standing wave patterns on the Cu(111) surface serve to monitor the local electronic perturbation caused by the interaction of the wire end with the step edge, giving information on the quality of the contact.

STM control of chemical reaction: single-molecule synthesis.

The fascinating advances in single atom/molecule manipulation with a scanning tunneling microscope (STM) tip allow scientists to fabricate atomic-scale structures or to probe chemical and physical properties of matters at an atomic level. Owing to these advances, it has become possible for the basic chemical reaction steps, such as dissociation, diffusion, adsorption, readsorption, and bond-formation processes, to be performed by using the STM tip. Complete sequences of chemical reactions are able to induce at a single-molecule level. New molecules can be constructed from the basic molecular building blocks on a one-molecule-at-a-time basis by using a variety of STM manipulation schemes in a systematic step-by-step manner. These achievements open up entirely new opportunities in nanochemistry and nanochemical technology. In this review, various STM manipulation techniques useful in the single-molecule reaction process are reviewed, and their impact on the future of nanoscience and technology are discussed.

Surface-state depopulation on small Ag(111) terraces.

The dependence of the local density of states near the Fermi energy E(F) on the width of terraces T is investigated by tunneling scanning spectroscopy on Ag(111) at 7 K. With decreasing T, the electronic density in the occupied surface state shifts monotonically towards E(F), leading to a depopulation at T=3.2 nm in quantitative agreement with a Fabry-Pérot model. Depopulation coincides with a switch from confinement by terrace modulation to step modulation.