Controlling water dissociation on an ultrathin MgO film by tuning film thickness

Periodic density-functional theory calculations at the single-molecule level were used to study dissociation of water on ultrathin MgO films with varying thickness deposited on the Ag(100) surface. The enhanced chemical activity for water dissociation on MgO/Ag(100) originates from the greater stability of dissociated products, which is due in turn to the strong hybridization of their electronic states at the oxide-metal interface. Our results provide insights into the superiority of the monolayer MgO film surface over the bulk surface and the use of the film thickness to control heterogeneous catalysis in water dissociation.open11

Electronic structure of single-walled carbon nanotubes on ultrathin insulating films

The electronic structures of single-walled carbon nanotubes on Ag(100) and on ultrathin insulating NaCl(100)/Ag(100) were studied using low-temperature scanning tunneling microscopy. The Fermi level of the nanotubes was shifted toward the conduction band on Ag(100), while it was shifted toward the valence band on NaCl films. We explain this opposite behavior by different basic mechanisms accounting for the Fermi level shifts. On the metal surface, the work function difference between the tube and the substrate determines the direction of the Fermi level shift. In the case of carbon nanotubes on insulating films, the electric field resulting from the dipole moment formed at the interface between the insulating film and the metal plays a decisive role in determining the Fermi level.open8

Lateral Hopping of CO on Ag(110) by Multiple Overtone Excitation

A novel type of action spectrum representing multiple overtone excitations of the upsilon(M-C) mode was observed for lateral hopping of a CO molecule on Ag(110) induced by inelastically tunneled electrons from the tip of a scanning tunneling microscope. The yield of CO hopping shows sharp increases at 261 +/- 4 mV, corresponding to the C-O internal stretching mode, and at 61 +/- 2, 90 +/- 2, and 148 +/- 7 mV, even in the absence of corresponding fundamental vibrational modes. The mechanism of lateral CO hopping on Ag (110) was explained by the multistep excitation of overtone modes of upsilon(M-C) based on the numerical fitting of the action spectra, the nonlinear dependence of the hopping rate on the tunneling current, and the hopping barrier obtained from thermal diffusion experiments.ope

Identification of an AgS2 Complex on Ag(110)

Adsorbed sulfur has been investigated on the Ag(110) surface at two different coverages, 0.02 and 0.25 monolayers. At the lower coverage, only sulfur adatoms are present. At the higher coverage, there are additional bright features which we identify as linear, independent AgS2 complexes. This identification is based upon density functional theory (DFT) and its comparison with experimental observations including bias dependence and separation between complexes. DFT also predicts the absence of AgS2 complexes at low coverage, and the development of AgS2 complexes around a coverage of 0.25 monolayers of sulfur, as is experimentally observed. To our knowledge, this is the first example of an isolated linear sulfur-metal-sulfur complex

Electronic modulations in a single wall carbon nanotube induced by the Au(111) surface reconstruction

The structural and electronic structure of single wall carbon nanotubes adsorbed on Au(111) has been investigated by low-temperature scanning tunneling microscopy and spectroscopy. The nanotubes were dry deposited in situ in ultrahigh vacuum onto a perfectly clean substrate. In some cases, the native herringbone reconstruction of the Au(111) surface interacted directly with adsorbed nanotubes and produced long-range periodic oscillations in their local density of states, corresponding to charge transfer modulations along the tube axis. This effect, however, was observed not systematically for all tubes and only for semiconducting tubes. © 2015 AIP Publishing LLCclose0

Communication: Structure, formation, and equilibration of ensembles of Ag-S complexes on an Ag surface

We have utilized conditions of very low temperature (4.7 K) and very low sulfur coverage to isolate and identify Ag-S complexes that exist on the Ag(111) surface. The experimental conditions are such that the complexes form at temperatures above the temperature of observation. These complexes can be regarded as polymeric chains of varying length, with an Ag4S pyramid at the core of each monomeric unit. Steps may catalyze the formation of the chains and this mechanism may be reflected in the chain length distribution

Search for the Structure of a Sulfur-Induced Reconstruction on Cu(111)

We have carried out an extensive DFT-based search for the structure of the (√43 × √43)R ± 7.5° reconstruction of S on Cu(111), which exhibits a honeycombtype structure in scanning tunneling microscopy (STM). We apply two criteria in this search: The structure must have a reasonably low chemical potential, and it must provide a good match with STM data, both our own and the data published by Wahlström et al. Phys. Rev. B 1999, 60, 10699. The best model has 12 S adatoms and 9 Cu adatoms per unit cell. Local defects within the Cu9S12 framework, consisting of one missing or one extra Cu adatom per unit cell, would be difficult to detect with STM and would not be energetically costly. There is no obvious correlation between this model and the structure of bulk CuS. If the √43 reconstruction is viewed in terms of local building blocks, then CuS3 and CuS2 clusters, linked by shared S atoms, provides the best description