A tight-binding model for MoS2 monolayers.

We propose an accurate tight-binding parametrization for the band structure of MoS2 monolayers near the main energy gap. We introduce a generic and straightforward derivation for the band energies equations that could be employed for other monolayer dichalcogenides. A parametrization that includes spin-orbit coupling is also provided. The proposed set of model parameters reproduce both the correct orbital compositions and location of valence and conductance band in comparison with ab initio calculations. The model gives a suitable starting point for realistic large-scale atomistic electronic transport calculations.

Segregation of Fischer-Tropsch reactants on cobalt nanoparticle surfaces.

Using scanning tunnelling microscopy, we have visualized the segregation of carbon monoxide and hydrogen, the two reactants in Fischer-Tropsch synthesis, on cobalt nanoparticles at catalytically relevant coverages. Density functional theory was used to interrogate the relevant energetics.

Electronic properties and charge transfer phenomena in Pt nanoparticles on γ-Al2O3: size, shape, support, and adsorbate effects.

This study presents a systematic detailed experimental and theoretical investigation of the electronic properties of size-controlled free and γ-Al(2)O(3)-supported Pt nanoparticles (NPs) and their evolution with decreasing NP size and adsorbate (H(2)) coverage. A combination of in situ X-ray absorption near-edge structure (XANES) and density functional theory (DFT) calculations revealed changes in the electronic characteristics of the NPs due to size, shape, NP-adsorbate (H(2)) and NP-support interactions. A correlation between the NP size, number of surface atoms and coordination of such atoms, and the maximum hydrogen coverage stabilized at a given temperature is established, with H/Pt ratios exceeding the 1 : 1 ratio previously reported for bulk Pt surfaces.

Atom-by-atom extraction using the scanning tunneling microscope tip-cluster interaction.

We investigate the atomistic details of a single atom-extraction process realized by using the scanning tunneling microscope tip-cluster interaction on a Ag(111) surface at 6 K. Single atoms are extracted from a silver cluster one atom at a time using small tunneling biases less than 35 mV. Combined total energy calculations and molecular dynamics simulations show a lowering of the atom-extraction barrier upon approaching the tip to the cluster. Thus, a mere tuning of the proximity between the tip and the cluster governs the extraction process. The atomic precision and reproducibility of this procedure are demonstrated by repeatedly extracting single atoms from a silver cluster on an atom-by-atom basis.

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.

Halogen-substituted thiophenol molecules on Cu(111).

Para-halosubstituted thiophenols (X-TPs, where X is Br, Cl, or F) form ordered islands and monolayers on Cu(111) at temperatures as low as 81 K. At incomplete coverages, all X-TPs adsorb with the dehydrogenated thiol group attached to the substrate and the substituted ring inclined toward the surface, as verified experimentally and theoretically. The structure of ordered islands has a pronounced dependence on the nature of the halogen substituent: while unsubstituted TP and pentafluoro-TP molecules do not self-assemble into extended ordered patterns at 81 K, X-TP molecules form a range of different structures which depend both on the size and electronegativity of the substituent, as well as on the coverage.

Optical recognition of atomic steps on surfaces.

Visible and UV light spectra display striking differences in optical reflectivity for the two types of monatomic steps on copper (111) surfaces. Electronic structure calculations trace these differences to the specific contributions of p(axially) and p(radially) local densities of states, parallel and perpendicular to the steps, of the distinctly coordinated corner atoms. The local origin of the spectral reflectance anisotropy is further corroborated by experiments on Cu(111) surfaces with varying step densities. Site specificity of the electronic structure of atoms in low coordinated sites on Cu(111) vicinals is thus revealed by reflectance anisotropy spectroscopy which can thereby detect step atom densities down to 10(13) atoms/cm(2).

Validity of the quasiharmonic analysis for surface thermal expansion of Ag(111).

For temperatures above 0.6T(m) (the bulk melting temperature) we show that the quasiharmonic approximation leads to increasingly larger values of the surface thermal expansion of Ag(111) as compared to that obtained from molecular dynamics simulations based on fully anharmonic interaction potentials. The inadequacy of the quasiharmonic approximation is traced to the excessive softening of the surface phonon frequencies. We discuss the validity of the quasiharmonic approximation for surfaces at elevated temperature, in view of recent x-ray scattering data on Ag(111).