Vibrational dynamics and surface structure of Bi(111) from helium atom scattering measurements.

The Bi(111) surface was studied by elastic scattering of helium atoms at temperatures between 118 and 423 K. The observed diffraction patterns with clear peaks up to third order were used to model the surface corrugation using the eikonal approximation as well as the GR method. Best fit results were obtained with a rather large corrugation height compared to other surfaces with metallic character. The corrugation shows a slight enhancement of the surface electron density in between the positions of the surface atoms. The vibrational dynamics of Bi(111) were investigated by measurements of the Debye-Waller attenuation of the elastic diffraction peaks and a surface Debye temperature of (84 ± 8) K was determined. A decrease of the surface Debye temperature at higher temperatures that was recently observed on Bi nanofilms could not be confirmed in the case of our single-crystal measurements.

Coexistence of negatively and positively buckled isomers on n+-doped Si(111) − 2 × 1.

A long-standing puzzle regarding the Si(111) − 2 × 1 surface has been solved. The surface energy gap previously determined by photoemission on heavily n-doped crystals was not compatible with a strongly bound exciton known from other considerations to exist. New low-temperature angle-resolved photoemission and scanning tunneling microscopy data, together with theory, unambiguously reveal that isomers with opposite bucklings and different energy gaps coexist on such surfaces. The subtle energetics between the isomers, dependent on doping, leads to a reconciliation of all previous results.

Elastic and inelastic scattering of He atoms from Bi(111).

Elastic and inelastic scattering of helium atoms has been used to study the Bi(111) surface. Sharp diffraction peaks are found with results in excellent agreement with previous structure determinations of the Bi(111) surface. The rather large first order peaks with respect to the zero order peak indicate a stronger surface corrugation than observed in helium scattering from other metallic surfaces. Time-of-flight spectra of scattered He atoms clearly reveal two inelastic scattering maxima, which allow a first report on phonon creation and annihilation events on the Bi(111) surface. An estimate of the group velocity shows that the phonon creation peak is likely to correspond to a Rayleigh mode.

Direct evidence for the effect of quantum confinement of surface-state electrons on atomic diffusion.

We report on the direct observations of the effect of quantum confinement of surface-state electrons on atomic diffusion. Confined electronic states induced by open nanoscale resonators [consisting of two parallel monatomic Cu chains on Cu(111)] are studied by means of scanning tunneling microscope measurements and first-principles calculations. Strongly anisotropic diffusion of adatoms around and inside resonators is revealed at low temperatures. The formation of diffusion channels and empty zones is demonstrated. We show that it is possible to engineer atomic diffusion by varying the distance between the resonator walls.

Achieving epitaxy between incommensurate materials by quasicrystalline interlayers.

Epitaxial interfaces of commensurate periodic materials can be characterized by a locking into registry of their atomic structure. This characteristic is identified as a natural framework to capture the essence of epitaxy also for systems including quasicrystalline materials. The resulting general definition for epitaxy requires a matching of reciprocal lattice points. The consequences for the real space structure of an epitaxial interface between quasiperiodic and periodic materials are explored and an experimental realization of such an interface is presented. It is demonstrated that due to their higher number of reciprocal lattice basis vectors (exceeding three), quasicrystals can provide interlayers epitaxially linking incommensurate materials.

Electron induced ortho-meta isomerization of single molecules.

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.

Surface phase transition in H/W(110) induced by tuning the fermi surface nesting vector by hydrogen loading.

At a hydrogen coverage of one monolayer, W(110) is known to exhibit a Fermi nesting in its electronic surface states with a nesting vector q{N} of 0.9 A{-1} along [001]. Here we show that additional H adsorption allows a controlled tuning of q{N}. As q{N} approaches the commensurate value of 1.0 A{-1}, its signature in inelastic He-atom scattering becomes more pronounced, finally disappearing as a surface charge density wave (CDW) develops and the surface symmetry changes from c(2 x 2) to a p(8 x 2) superstructure. The gradual change in q{N} is attributed to an energetic shift of the spin-polarized electronic surface states that eventually form the surface CDW.

Decompositional incommensurate growth of ferrocene molecules on a Au(111) surface.

Deviating from the common growth mode of molecular films of organic molecules where the adsorbates remain intact, we observe an essentially different growth behavior for metallocenes with a low temperature scanning tunneling microscope. Ferrocene molecules adsorb dissociatively and form a two layer structure. The top layer unit cell is composed of two tilted cyclopentadienyl (cp) rings, while the first layer consists of ferrocene molecules and cp-Fe complexes. Surprisingly a fourfold symmetry is observed for the top layer while the first layer displays threefold symmetry elements. It is this symmetry mismatch which induces an incommensurability between these layers in all except one surface direction. The top layer is weakly bonded and has an antiferromagnetic ground state as calculated by local spin density functional approximation.

Quasicrystalline epitaxial single element monolayers on icosahedral Al-pd-mn and decagonal Al-ni-co quasicrystal surfaces.

Single element quasicrystalline monolayers were prepared by deposition of antimony and bismuth on the fivefold surface of icosahedral Al71.5Pd21Mn8.5 and the tenfold surface of decagonal Al71.8Ni14.8Co13.4. Elastic helium atom scattering and low energy electron diffraction of the monolayers show Bragg peaks at the bulk derived positions of the clean surfaces, revealing highly ordered quasicrystalline epitaxial films. Their adatom densities of (0.9+/-0.2)x10(15) cm(-2) and (0.8+/-0.2)x10(15) cm(-2) on Al-Pd-Mn and Al-Ni-Co, respectively, correspond to roughly one adatom per Al atom of the quasicrystalline substrate surfaces.

Atomic-scale structure of dislocations revealed by scanning tunneling microscopy and molecular dynamics.

The intersection between dislocations and a Ag(111) surface has been studied using an interplay of scanning tunneling microscopy (STM) and molecular dynamics. Whereas the STM provides atomically resolved information about the surface structure and Burgers vectors of the dislocations, the simulations can be used to determine dislocation structure and orientation in the near-surface region. In a similar way, the subsurface structure of other extended defects can be studied. The simulations show dislocations to reorient the partials in the surface region leading to an increased splitting width at the surface, in agreement with the STM observations. Implications for surface-induced cross slip are discussed.

Engineering electronic lifetimes in artificial atomic structures.

By means of atomic manipulation, 51 Ag atoms have been precisely positioned to form a triangle with a base length of 245 A on a Ag(111) substrate. The scattering of the surface electrons at these adatoms results in a complex interference pattern. Spectroscopic data and dI/dV maps taken inside the triangle have been quantitatively evaluated by multiple scattering calculations of the wave pattern. Adjustment of the scattering parameters to the data yields the properties of the scatterers and the electron lifetimes. The experimental results for the electron lifetimes deviate from a (E-E(F))(-2) dependence and reflect the electronic band structure at the surface as well as the local influence of the triangle.

High frequency surface vibrational modes and relaxation of MgO nanocrystals.

We present a computational proof for the puzzling experimental vibrational density of states in MgO nanocrystals measured by neutron scattering. For the first time, the experimental peak of longitudinal optical modes in the high frequency region is theoretically reproduced and traced back to surface inward relaxation. Practically perfect agreement of theory with the experiment demonstrates the importance of nanocrystal size effects. Dependence of the transversal optical model on the volume/surface ratio is also verified. Strong (up to 2%) buckling of nanocrystal faces is found. Our calculations show varieties of relaxation shapes for clusters, shedding light on contradictory data on nanocrystals and infinite surfaces.

Recording intramolecular mechanics during the manipulation of a large molecule.

The technique of single atom manipulation by means of the scanning tunneling microscope (STM) applies to the controlled displacement of large molecules. By a combined experimental and theoretical work, we show that in a constant height mode of manipulation the STM current intensity carries detailed information on the internal mechanics of the molecule when guided by the STM tip. Controlling and time following the intramolecular behavior of a large molecule on a surface is the first step towards the design of molecular tunnel-wired nanorobots.

Ionic films on vicinal metal surfaces: enhanced binding due to charge modulation.

NaCl films on Cu(311) exhibit a remarkably strong and localized binding between adlayer and substrate. The binding sites of the ions in the NaCl film with respect to the Cu surface are determined from atomically resolved scanning tunneling microscopy images. A new model is proposed in which the binding mechanism is controlled by the charge modulation of a regularly stepped surface due to the Smoluchowski effect. This model can be extended to explain the growth of ionic adlayers on regularly stepped and kinked metal surfaces in general.

Conformational changes of single molecules induced by scanning tunneling microscopy manipulation: a route to molecular switching.

A detailed experimental and theoretical investigation of the processes involved in the manipulation of individual specially designed porphyrin-based molecules by scanning tunneling microscopy at low temperature is presented. On a stepped Cu(211) surface, the interaction between tip and molecule was used to locally modify in a reversible way the internal configuration of a single molecule, thus drastically changing the tunneling current passing through it. Model calculations confirm that this manipulation realizes the principle of a conformational molecular switch.

Inducing single-molecule chemical reactions with a UHV-STM: a new dimension for nano-science and technology.

Atomic and molecular manipulations with the scanning tunnelling microscope (STM) lead to many fascinating advances during the last decade. Recent achievements in inducing all of the basic steps of a chemical reaction with the STM at a single-molecule level open up entirely new opportunities in chemistry on the nanoscale. In this article, we review various STM-based molecular manipulation techniques and their application in inducing all elementary chemical reaction steps on surfaces. Prospects for future opportunities of single-molecule chemical engineering and their possible implications to nanoscale science and technology are discussed.

Substrate mediated long-range oscillatory interaction between adatoms: Cu /Cu(111).

A quantitative study of the long-range interaction between single copper adatoms on Cu(111) mediated by the electrons in the two-dimensional surface-state band is presented. The interaction potential was determined by evaluating the distance distribution of two adatoms from a series of scanning tunneling microscopy images taken at temperatures of 9-21 K. The long-range interaction is oscillatory with a period of half the Fermi wavelength and decays for larger distances d as 1/d(2). Five potential minima were identified for separations of up to 70 A. The interaction significantly changes the growth of Cu/Cu(111) at low temperatures.