Surface microscopy using vacuum tunneling is demonstrated for the first time. Topographic pictures of surfaces on an atomic scale have been obtained. Examples of resolved monoatomic steps and surface reconstructions are shown for (110) surfaces of CaIrSn 4 and Au.

https://link.aps.org/pdf/10.1103/PhysRevLett.49.57

Surface studies by scanning tunneling microscopy

Molybdenum disulfide (MoS2) of single- and few-layer thickness was exfoliated on SiO2/Si substrate and characterized by Raman spectroscopy. The number of S−Mo−S layers of the samples was independently determined by contact-mode atomic force microscopy. Two Raman modes, E12g and A1g, exhibited sensitive thickness dependence, with the frequency of the former decreasing and that of the latter increasing with thickness. The results provide a convenient and reliable means for determining layer thickness with atomic-level precision. The opposite direction of the frequency shifts, which cannot be explained solely by van der Waals interlayer coupling, is attributed to Coulombic interactions and possible stacking-induced changes of the intralayer bonding. This work exemplifies the evolution of structural parameters in layered materials in changing from the three-dimensional to the two-dimensional regime.

/pdf/anomalous-lattice-vibrations-of-single-and-few-layer-mos2-1w8dp2s904.pdf

Anomalous lattice vibrations of single- and few-layer MoS2.

5.1. Nanoalloys of Group 11 (Cu, Ag, Au) 865 5.1.1. Cu−Ag 866 5.1.2. Cu−Au 867 5.1.3. Ag−Au 870 5.1.4. Cu−Ag−Au 872 5.2. Nanoalloys of Group 10 (Ni, Pd, Pt) 872 5.2.1. Ni−Pd 872 * To whom correspondence should be addressed. Phone: +39010 3536214. Fax:+39010 311066. E-mail: ferrando@fisica.unige.it. † Universita di Genova. ‡ Argonne National Laboratory. § University of Birmingham. | As of October 1, 2007, Chemical Sciences and Engineering Division. Volume 108, Number 3

Nanoalloys: From Theory to Applications of Alloy Clusters and Nanoparticles

Colloidal metal nanoparticles are emerging as key materials for catalysis, plasmonics, sensing, and spectroscopy. Within these applications, control of nanoparticle shape lends increasing functionality and selectivity. Shape-controlled nanocrystals possess well-defined surfaces and morphologies because their nucleation and growth are controlled at the atomic level. An overall picture of shaped metal particles is presented, with a particular focus on solution-based syntheses for the noble metals. General strategies for synthetic control are discussed, emphasizing key factors that result in anisotropic, nonspherical growth such as crystallographically selective adsorbates and seeding processes.

/pdf/shape-control-of-colloidal-metal-nanocrystals-33lclmees7.pdf

Shape Control of Colloidal Metal Nanocrystals

https://th.fhi-berlin.mpg.de/site/uploads/Publications/CPC-180-2175-2009.pdf

Ab Initio Molecular Simulations with Numeric Atom-Centered Orbitals

A general formalism is developed by means of which the radiative heat transfer between macroscopic bodies of arbitrary dispersive and absorptive dielectric properties can be evaluated. The general formalism is applied to the heat transfer across a vacuum gap between two identical semi-infinite bodies at different temperatures. The peculiarities arising when the gap width is of the order of, or smaller than, the dominant thermal radiation wavelengths are studied and quantitatively evaluated for the case of two metal bodies. The predicted strong increase with diminishing gap width is in qualitative agreement with experimental results.

Theory of Radiative Heat Transfer between Closely Spaced Bodies

https://escholarship.org/content/qt5ms12246/qt5ms12246.pdf

The surface reconstructions of the (100) crystal faces of iridium, platinum and gold. I. Experimental observations and possible structural models

The location of a half monolayer of ordered hydrogen adatoms on Ni(111) has been analyzed by Low‐Energy Electron Diffraction (LEED), Thermal Desorption Spectroscopy (TDS), and Work Function (Δφ) measurements. It is found that the hydrogen atoms are arranged in an overlayer of graphitic structure with a (2×2) unit cell with respect to the substrate unit cell. In the ordered regions, the hydrogen adatoms occupy both types of three fold hollow sites without a detectable difference in the Ni–H bond lengths between the two sites. The Ni–H bond length is found to be 1.84±0.06 A, corresponding to an overlayer‐substrate spacing of 1.15±0.1 A. The relation between this structure and its observed order–disorder phase diagram as a function of temperature and hydrogen coverage is discussed. The disorder is discussed in detail, and a novel ’’atomic band structure’’ interpretation is given.

Chemisorption geometry of hydrogen on Ni(111): Order and disorder

Adsorption of CO on a Pd(100) surface was studied in detail mainly by LEED, UPS, work function and thermal desorption measurements. Analysis of the ordered c(2√2×√2) R 45° structure occurring at Θ=0.5 revealed that in this phase each CO molecule is bridge bonded to 2 Pd atoms with Pd–C distances of 1.93±0.07 A and a C–O bond length of 1.15±0.1 A, the molecular axis being oriented normal to the surface. The mutual configuration of the adsorbed molecules is explained in terms of a short‐range repulsive interaction model, which is supported by the observation that the isosteric heat of adsorption (Ead=38.5 kcal/mole) is constant up to a coverage of Θ?0.45. The photoelectron spectra exhibit two maxima at 7.9 (5σ+1π level) and 10.8 eV (4σ level) below the Fermi level which are in agreement with the observations with other Pd planes. This also holds for an electronic excitation associated with an energy of 13.5 eV as observed by electron energy loss spectroscopy. The variation of the sticking coefficient with coverage is described in terms of a second‐order precursor state model with repulsive interactions. The pre‐exponential factor for desorption (3×1016 sec−1) varies only little with coverage. The dipole moment of the adsorbate remains constant up to Θ?0.35 (0.17 D) where the overlayer starts to order, and exhibits an appreciable higher value near Θ=0.5. The maximum work function increase is Δφmax=0.93 V at Θ=0.5. The differential entropy of the adsorbed layer around 450 K was derived from the experimental adsorption isotherms. Up to Θ=0.35 the data fall well between the limits of two theoretical models for localised and delocalised adsorption of noninteracting particles. Deviations at higher coverages reflect again the onset of ordering. The energetic and work function data are in some variance to results reported earlier which is ascribed to the fact that these quantities may be sensitively influenced by spurious amounts of carbon impurities on the surface.

M. A. Van Hove

Papers

Theory of Radiative Heat Transfer between Closely Spaced Bodies

The surface reconstructions of the (100) crystal faces of iridium, platinum and gold. I. Experimental observations and possible structural models

Chemisorption geometry of hydrogen on Ni(111): Order and disorder

Adsorption of CO on Pd(100)

Adsorbate-induced restructuring of surfaces