Energy dependence of abstractive versus dissociative chemisorption of fluorine molecules on the silicon (111)-(7x7) surface

Scanning tunneling microscopy and monoenergetic molecular beams have been used to obtain real-space atomic images of the competition between abstractive and dissociative chemisorption. The size distribution of Si-F adsorbates on the Si(111)-(7x7) surface was examined as a function of the incident translational energy of the F(2) molecules. For F(2) molecules with 0.03 electron volt of incident energy, the dominant adsorbate sites were isolated Si-F species. As an F(2) molecule with low translational energy collides with the surface, abstraction occurs and only one of the F atoms chemisorbs; the other is ejected into the gas phase. For F(2) molecules with 0.27 electron volt of incident energy, many adjacent Si-F adsorbates (dimer sites) were observed because F(2) molecules with high translational energy collide with the surface and chemisorb dissociatively so that both F atoms react to form adjacent Si-F adsorbates. For halogens with very high incident energy (0.5-electron volt Br(2)), dissociative chemisorption is the dominant adsorption mechanism and dimer sites account for nearly all adsorbates.     

Visualization and spectroscopy of a metal-molecule-metal bridge

Artificial nanostructures, each composed of a copper(II) phthalocyanine (CuPc) molecule bonded to two gold atomic chains with a controlled gap, were assembled on a NiAl(110) surface by manipulation of individual gold atoms and CuPc molecules with a scanning tunneling microscope. The electronic densities of states of these hybrid structures were measured by spatially resolved electronic spectroscopy and systematically tuned by varying the number of gold atoms in the chains one by one. The present approach provides structural images and electronic characterization of the metal-molecule-metal junction, thereby elucidating the nature of the contacts between the molecule and metal in this junction.     

Single-bond formation and characterization with a scanning tunneling microscope

A scanning tunneling microscope (STM) was used to manipulate the bonding of a carbon monoxide (CO) molecule and to analyze the structure and vibrational properties of individual products. Individual iron (Fe) atoms were evaporated and coadsorbed with CO molecules on a silver (110) surface at 13 kelvin. A CO molecule was transferred from the surface to the STM tip and bonded with an Fe atom to form Fe(CO). A second CO molecule was similarly transferred and bonded with Fe(CO) to form Fe(CO)(2). Controlled bond formation and characterization at the single-bond level probe chemistry at the spatial limit.     

Controlled atomic doping of a single C60 molecule

We report a method for controllably attaching an arbitrary number of charge dopant atoms directly to a single, isolated molecule. Charge-donating K atoms adsorbed on a silver surface were reversibly attached to a C60 molecule by moving it over K atoms with a scanning tunneling microscope tip. Spectroscopic measurements reveal that each attached K atom donates a constant amount of charge (approximately 0.6 electron charge) to the C60 host, thereby enabling its molecular electronic structure to be precisely and reversibly tuned.     

Current-induced hydrogen tautomerization and conductance switching of naphthalocyanine molecules

The bistability in the position of the two hydrogen atoms in the inner cavity of single free-base naphthalocyanine molecules constitutes a two-level system that was manipulated and probed by low-temperature scanning tunneling microscopy. When adsorbed on an ultrathin insulating film, the molecules can be switched in a controlled fashion between the two states by excitation induced by the inelastic tunneling current. The tautomerization reaction can be probed by resonant tunneling through the molecule and is expressed as considerable changes in the conductivity of the molecule. We also demonstrated a coupling of the switching process so that the charge injection in one molecule induced tautomerization in an adjacent molecule.     

X-ray diffraction and computation yield the structure of alkanethiols on gold(111)

The structure of self-assembled monolayers (SAMs) of long-chain alkyl sulfides on gold(111) has been resolved by density functional theory-based molecular dynamics simulations and grazing incidence x-ray diffraction for hexanethiol and methylthiol. The analysis of molecular dynamics trajectories and the relative energies of possible SAM structures suggest a competition between SAM ordering, driven by the lateral van der Waals interaction between alkyl chains, and disordering of interfacial Au atoms, driven by the sulfur-gold interaction. We found that the sulfur atoms of the molecules bind at two distinct surface sites, and that the first gold surface layer contains gold atom vacancies (which are partially redistributed over different sites) as well as gold adatoms that are laterally bound to two sulfur atoms.     

Ti8C12+-Metallo-Carbohedrenes: A New Class of Molecular Clusters?

During the course of studying the dehydrogenation reactions of hydrocarbons by titanium atoms, ions, and clusters, an exceptionally stable and abundant cluster which contains 8 titaniums and 12 carbons was discovered. "Titration" reactions with ND(3) reveal the uptake of eight molecules, pointing to the fact that the titanium atoms are at exposed positions of similar coordination. A dodecahedral structure of T(h) point group symmetry is proposed to account for the unusual stability of this molecular cluster. The Ti(8)C(12)(+) dodecahedron has 12 pentagonal rings and each of the rings is formed by two titanium and three carbon atoms, where each titanium is bound to three carbons. Based on the model, it is expected that neutral Ti(8)C(12) would be a stable metallo-carbododecahedral molecule and may comprise one member of a new class of molecules, namely metallo-carbohedrenes.     

A homonuclear molecule with a permanent electric dipole moment

Permanent electric dipole moments in molecules require a breaking of parity symmetry. Conventionally, this symmetry breaking relies on the presence of heteronuclear constituents. We report the observation of a permanent electric dipole moment in a homonuclear molecule in which the binding is based on asymmetric electronic excitation between the atoms. These exotic molecules consist of a ground-state rubidium (Rb) atom bound inside a second Rb atom electronically excited to a high-lying Rydberg state. Detailed calculations predict appreciable dipole moments on the order of 1 Debye, in excellent agreement with the observations.     

Controlling the Kondo effect of an adsorbed magnetic ion through its chemical bonding

We report that the Kondo effect exerted by a magnetic ion depends on its chemical environment. A cobalt phthalocyanine molecule adsorbed on an Au111 surface exhibited no Kondo effect. Cutting away eight hydrogen atoms from the molecule with voltage pulses from a scanning tunneling microscope tip allowed the four orbitals of this molecule to chemically bond to the gold substrate. The localized spin was recovered in this artificial molecular structure, and a clear Kondo resonance was observed near the Fermi surface. We attribute the high Kondo temperature (more than 200 kelvin) to the small on-site Coulomb repulsion and the large half-width of the hybridized d-level.     

Dissociation of individual molecules with electrons from the tip of a scanning tunneling microscope

The scanning tunneling microscope (STM) can be used to select a particular adsorbed molecule, probe its electronic structure, dissociate the molecule by using electrons from the STM tip, and then examine the dissociation products. These capabilities are demonstrated for decaborane(14) (B(10)H(14)) molecules adsorbed on a silicon(111)-(7 x 7) surface. In addition to basic studies, such selective dissociation processes can be used in a variety of applications to control surface chemistry on the molecular scale.     

A molecule carrier

We found that anthraquinone diffuses along a straight line across a flat, highly symmetric Cu111 surface. It can also reversibly attach one or two CO2 molecules as "cargo" and act as a "molecule carrier," thereby transforming the diffusive behavior of the CO2 molecules from isotropic to linear. Density functional theory calculations indicated a substrate-mediated attraction of approximately 0.12 electron volt (eV). Scanning tunneling microscopy revealed individual steps of the molecular complex on its diffusion pathway, with increases of approximately 0.03 and approximately 0.02 eV in the diffusion barrier upon attachment of the first and second CO2 molecule, respectively.     

Structure of an oxygen-carrying cobalt complex

Bis(3-fluorosalicylaldehyde) ethylenediimine cobalt(II), a reversible oxygen-carrying compound, has been crystallized as a tetramer with two oxygen molecules bound to the four cobalt atomns, each oxygen molecule bridging between two metal atoms. These dimers are further linked by two bonds between the oxygen atom of the salicylaldehyde and the cobalt atom. The oxygen-to-oxygen distance, 1.21 angstroms in molecular oxygen, has increased to 1.308(28) angstroms (where the number in parentheses is the estimated standard deviation) in this compound, the shortest distance yet observed in sutch a bridging arrangement.     

Molecule cascades

Carbon monoxide molecules were arranged in atomically precise configurations, which we call "molecule cascades," where the motion of one molecule causes the subsequent motion of another, and so on in a cascade of motion similar to a row of toppling dominoes. Isotopically pure cascades were assembled on a copper (111) surface with a low-temperature scanning tunneling microscope. The hopping rate of carbon monoxide molecules in cascades was found to be independent of temperature below 6 kelvin and to exhibit a pronounced isotope effect, hallmarks of a quantum tunneling process. At higher temperatures, we observed a thermally activated hopping rate with an anomalously low Arrhenius prefactor that we interpret as tunneling from excited vibrational states. We present a cascade-based computation scheme that has all of the devices and interconnects required for the one-time computation of an arbitrary logic function. Logic gates and other devices were implemented by engineered arrangements of molecules at the intersections of cascades. We demonstrate a three-input sorter that uses several AND gates and OR gates, as well as the crossover and fan-out units needed to connect them.     

Manipulation of adsorbed atoms and creation of new structures on room-temperature surfaces with a scanning tunneling microscope

A general method of manipulating adsorbed atoms and molecules on room-temperature surfaces with the use of a scanning tunneling microscope is described. By applying an appropriate voltage pulse between the sample and probe tip, adsorbed atoms can be induced to diffuse into the region beneath the tip. The field-induced diffusion occurs preferentially toward the tip during the voltage pulse because of the local potential energy gradient arising from the interaction of the adsorbate dipole moment with the electric field gradient at the surface. Depending upon the surface and pulse parameters, cesium (Cs) structures from one nanometer to a few tens of nanometers across have been created in this way on the (110) surfaces of gallium arsenide (GaAs) and indium antimonide (InSb), including structures that do not naturally occur.     

Water-mediated proton hopping on an iron oxide surface

The diffusion of hydrogen atoms across solid oxide surfaces is often assumed to be accelerated by the presence of water molecules. Here we present a high-resolution, high-speed scanning tunneling microscopy (STM) study of the diffusion of H atoms on an FeO thin film. STM movies directly reveal a water-mediated hydrogen diffusion mechanism on the oxide surface at temperatures between 100 and 300 kelvin. Density functional theory calculations and isotope-exchange experiments confirm the STM observations, and a proton-transfer mechanism that proceeds via an H(3)O(+)-like transition state is revealed. This mechanism differs from that observed previously for rutile TiO(2)(110), where water dissociation is a key step in proton diffusion.     

Divalent metal nanoparticles

Nanoparticles can be used as the building blocks for materials such as supracrystals or ionic liquids. However, they lack the ability to bond along specific directions as atoms and molecules do. We report a simple method to place target molecules specifically at two diametrically opposed positions in the molecular coating of metal nanoparticles. The approach is based on the functionalization of the polar singularities that must form when a curved surface is coated with ordered monolayers, such as a phase-separated mixture of ligands. The molecules placed at these polar defects have been used as chemical handles to form nanoparticle chains that in turn can generate self-standing films.     

Atomic-scale coupling of photons to single-molecule junctions

Spatial resolution at the atomic scale has been achieved in the coupling of light to single molecules adsorbed on a surface. Electron transfer to a single molecule induced by green to near-infrared light in the junction of a scanning tunneling microscope (STM) exhibited spatially varying probability that is confined within the molecule. The mechanism involves photo-induced resonant tunneling in which a photoexcited electron in the STM tip is transferred to the molecule. The coupling of photons to the tunneling process provides a pathway to explore molecular dynamics with the combined capabilities of lasers and the STM.     

Quantum gas of deeply bound ground state molecules

Molecular cooling techniques face the hurdle of dissipating translational as well as internal energy in the presence of a rich electronic, vibrational, and rotational energy spectrum. In our experiment, we create a translationally ultracold, dense quantum gas of molecules bound by more than 1000 wave numbers in the electronic ground state. Specifically, we stimulate with 80% efficiency, a two-photon transfer of molecules associated on a Feshbach resonance from a Bose-Einstein condensate of cesium atoms. In the process, the initial loose, long-range electrostatic bond of the Feshbach molecule is coherently transformed into a tight chemical bond. We demonstrate coherence of the transfer in a Ramsey-type experiment and show that the molecular sample is not heated during the transfer. Our results show that the preparation of a quantum gas of molecules in specific rovibrational states is possible and that the creation of a Bose-Einstein condensate of molecules in their rovibronic ground state is within reach.     

CHEMISTRY: Harnessing the Power of Diatomics

When a diatomic molecule is broken up into its constituent atoms, these very energetic atoms provide a large driving force for further reaction. Diatomic molecules often do not undergo productive chemistry, however, because the energy needed to break the diatomic bond is also high. In his Perspective, Thorp discusses the work by MacBeth et al., who have synthesized a nonheme iron complex that reacts with O2 to produce two equivalents of a metal-oxo complex. The complex elegantly mimic the ability of some enzymes to influence metal ion coordination spheres.     

Complement fixation on cell surfaces by 19S and 7S antibodies

The mechanism of complement fixation on cell surfaces by whole antiserums, and by 19S and 7S fractions has been studied with a new comple-ment-fixation test. This test is based on the fixation and transfer of the activated first component of complement (C1a). We have concluded that a single molecule of 19S antibody in combination with antigen at the cell surface is sufficient to bind one molecule of C1a. For 7S antibodies at least two molecules in close proximity at the cell surface are required to fix one molecule of C1a.