High-pressure (1 Torr) scanning tunneling microscopy (STM) study of the coadsorption and exchange of CO and NO on the Rh(111) crystal face

The coadsorption of CO and NO on Rh(111) at room temperature was studied with scanning tunneling microscopy (STM) in the catalytically relevant range of approximately 1 Torr. For gas mixtures where NO is not in large excess, a mixed layer with (2x2) structure is formed. The difference in binding energy between CO and NO on top sites was determined from the measured surface (by direct counting in STM images) and gas mole fractions of each species. A model for the molecular structure is proposed based on the analysis of exchange events between CO and NO molecules in the images. In this model as the partial pressure of NO increases, NO molecules occupy hollow sites first, by displacing CO, and top sites later, where they coexist with CO. As the surface fraction of NO increases, favorable NO-NO interactions cause the formation of segregated NO-rich regions. As with pure NO, a phase transition from the (2x2)-NO to the (3x3)-NO structure takes place in the NO-rich regions at high NO concentration. These results demonstrate the unique ability of STM to obtain molecular-level information under catalytic pressure conditions.     

A General Equation for Fitting Contact Area and Friction vs Load Measurements

The variation of contact area with load between adhesive elastic spheres depends upon the effective range of attractive surface forces. Relatively simple forms to describe limiting cases exist, but the general intermediate case requires a more complex analysis. Maugis, using a Dugdale model [D. Maugis, J. Colloid. Interf. Sci. 150, 243 (1992)], provides an analytic solution, but the resulting equations are cumbersome if one wishes to compare with experimental data such as atomic force microscope measurements. In this paper we present a simpler general equation that approximates Maugis' solution extremely closely. The general equation is amenable to conventional curve fitting software routines and provides a rapid method of determining the value of the "transition parameter" which describes the range of surface forces. Copyright 1999 Academic Press.     

The influence of sulfur adsorption on the step structure of vicinal Mo(100): a LEED and STM study

The effect of sulfur adsorption on the step structure of vicinal Mo(100) surfaces has been studied with scanning tunneling microscopy (STM) and low energy electron diffraction (LEED). STM was used for low densities of steps on a nominally flat (100) surface. LEED was used to study the more highly and regularly stepped (910), (911), and (28,4,1) oriented surfaces. Steps and the sulfur adsorbate were found to have a strong interaction. The presence and orientation of steps on the surface governed the formation of ordered domains of sulfur, and sulfur modified the structure of the steps on the surface. Both techniques show that monatomic steps predominate on the clean surfaces. When sulfur was adsorbed on the surfaces, however, steps coalesced to form groups of steps, double atomic height steps, and multiple height steps, depending on sulfur coverage and initial step density. The results are discussed in the framework of the theory of equilibrium crystal shape and provide information on how the Mo step-step interactions are affected by sulfur adsorption.     

Angular distributions of muon pairs produced by 194 GeV/c negative pions

We present the angular distributions of muon pairs obtained in a high-statistics experiment using a 194-GeV/c π^- impinging on a tungsten target. Our results are based on the analysis of 145,000 events with positive Feynmanx and mass above 4.07 GeV/c², excluding the ? region. Simple first-order QCD relations allow us to determine the ratio of annihilation with hard-gluon emission to the sum of annihilation with hard-gluon emission and hard-gluon Compton scattering, which is found to be about 58% to 75%. We determine the parton square intrinsic transverse momenta to be of the order of 0.6 (GeV/c)², and about 30% larger in the pion than in the nucleon. At largex ₁, our data agree with the higher-twist hypothesis, and support the interpretation of the relevant scale parameter as the dimuon square transverse momentum.     

Evidence for double dissociation in K-p interactions at 14.3 GeV/c

We have studied the reaction K^-p → K^-π⁺π^-π⁺π^-p at 14.3 GeV/c to search for evidence of the double dissociation process $\text{K}{}^{\mathrm{-}}\text{p}\text{→}\text{QN}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}{}^1$. In the channel $\text{K}{}^{\mathrm{-}}\text{p}\text{→}\text{K}{}^{10}\text{(890)}$π₁^-π₂^-Δ⁺⁺ (1236) there is evidence for simultaneous production of low-mass enhancements in the $\text{K}{}^{10}\text{π}{}_1{}^{\mathrm{-}}$ and Δ⁺⁺(1236)π₂^- subsystems which correspond to the $\text{Q}\text{→}\text{K}{}^1\text{(890)π}$ and $\text{N}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}{}^1\text{→ Δπ}$ decay modes. In this particular final state the double fragmentation system is produced with a cross section of the order of a few microbarns. Our data are consistent with the factorizable pomeron exchange model of double diffractive dissociation.     

A leed-aes study of the structure of sulfur monolayers on the Mo(100) crystal face

The formation of ordered phases of sulfur on the molybdenum (100) crystal face has been studied by Low Energy Electron Diffraction (LEED), Auger Electron Spectroscopy (AES) and Thermal Desorption Spectroscopies (TDS). Sulfur was deposited from a S₂ molecular flux streaming out of an Ag₂S containing electrochemical cell inside the UHV chamber. The use of a controlled flux of S₂ allowed the careful determination of saturation values for the monolayer, as well as the formation of multilayers of sulfur. This allowed the calibration of Auger intensities in terms of sulfur coverage. Various ordered structures, c(2 × 2), (1 × 2), $\text{2}\text{1}\text{?}\text{1}\text{1}$ and c(2 × 4), were observed by LEED for different values of the S coverage. Real space models for these structures are proposed that satisfy the coverage values observed and place sulfur atoms only on high symmetry four-fold sites on the (100) molybdenum surface.     

Mechanical and charge transport properties of alkanethiol self-assembled monolayers on a au(111) surface: the role of molecular tilt

The relationship between charge transport and mechanical properties of alkanethiol self-assembled monolayers (SAMs) on Au(111) films has been investigated using an atomic force microscope with a conductive tip. Molecular tilts induced by the pressure applied by the tip cause stepwise increases in film conductivity. A decay constant beta = 0.57 +/- 0.03 A-1 was found for the current passing through the film as a function of tip-substrate separation due to this molecular tilt. This is significantly smaller than the value of approximately 1 A-1 found when the separation is varied by changing the length of the alkanethiol molecules. Calculations indicate that, for isolated dithiol molecules S-bonded to hollow sites, the junction conductance does not vary significantly as a function of molecular tilt. The impact of S-Au bonding on SAM conductance is discussed.     

Photoelectron Spectroscopy at the Graphene–Liquid Interface Reveals the Electronic Structure of an Electrodeposited Cobalt/Graphene Electrocatalyst

Electrochemically grown cobalt on graphene exhibits exceptional performance as a catalyst for the oxygen evolution reaction (OER) and provides the possibility of controlling the morphology and the chemical properties during deposition. However, the detailed atomic structure of this hybrid material is not well understood. To elucidate the Co/graphene electronic structure, we have developed a flow cell closed by a graphene membrane that provides electronic and chemical information on the active surfaces under atmospheric pressure and in the presence of liquids by means of X‐ray photoelectron spectroscopy (XPS). We found that cobalt is anchored on graphene via carbonyl‐like species, namely Co(CO)_x, promoting the reduction of Co³⁺ to Co²⁺, which is believed to be the active site of the catalyst.     

In situ study of water-induced segregation of bromide in bromide-doped sodium chloride by scanning polarization force microscopy

The adsorption of water on Br-doped NaCl crystals has been studied in situ using scanning polarization force microscopy, a noncontact electrostatic atomic force microscopy operation mode. Both topography and contact potential images were acquired as a function of relative humidity at room temperature, from 0% to more than 55%. It was found that the surface of the freshly cleaved crystal has an inhomogeneous electrical surface potential distribution with the steps more negative than the terraces below 40% relative humidity. This difference disappears when the humidity reaches 40% and higher. Below 40% the step morphology experiences only small changes due to water adsorption; however, above 40% major changes take place due to solvation, segregation, and redistribution of lattice ions. Bromide-rich islands and crystallites segregate to the surface above 40% relative humidity followed by drying. These islands and crystallites have a negative surface potential relative to the rest of the surface. These effects are attributed to the preferential solvation and segregation of Br- ions.     

Autocatalytic water dissociation on Cu(110) at near ambient conditions

Autocatalytic dissociation of water on the Cu(110) metal surface is demonstrated on the basis of X-ray photoelectron spectroscopy studies carried out in situ under near ambient conditions of water vapor pressure (1 Torr) and temperature (275-520 K). The autocatalytic reaction is explained as the result of the strong hydrogen-bond in the H2O-OH complex of the dissociated final state, which lowers the water dissociation barrier according to the Br?nsted-Evans-Polanyi relations. A simple chemical bonding picture is presented which predicts autocatalytic water dissociation to be a general phenomenon on metal surfaces.