An insight into alkali promotion: a density functional theory study of CO dissociation on K/Rh(111)

The important role of alkali additives in heterogeneous catalysis is, to a large extent, related to the high promotion effect they have on many fundamental reactions. The wide application of alkali additives in industry does not, however, reflect a thorough understanding of the mechanism of their promotional abilities. To investigate the physical origin of the alkali promotion effect, we have studied CO dissociation on clean Rh(111) and K-covered Rh(111) surfaces using density functional theory. By varying the position of potassium atoms relative to a dissociating CO, we have mapped out the importance of different K effects on the CO dissociation reactions. The K-induced changes in the reaction pathways and reaction barriers have been determined; in particular, a large reduction of the CO dissociation barrier has been identified. A thorough analysis of this promotion effect allows us to rationalize both the electronic and the geometrical factors that govern alkali promotion effect: (i) The extent of barrier reductions depends strongly on how close K is to the dissociating CO. (ii) Direct K-O bonding that is in a very short range plays a crucial role in reducing the barrier. (iii) K can have a rather long-range effect on the TS structure, which could reduce slightly the barriers.

Effects of diphosphine structure on aurophilicity and luminescence in Au(I) complexes

The effects of diphosphine flexibility and bite angle on the structures and luminescence properties of Au(I) complexes have been investigated. A range of diphosphines based on heteroaromatic backbones [bis(2-diphenylphosphino)phenylether (dpephos), 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (xantphos), and 4,6-bis(diphenylphosphino)dibenzofuran (dbfphos)] has been used to prepare mono- and digold derivatives. A clear relationship between the presence of aurophilic contacts and the emission properties of dinuclear complexes has been observed, with one of the complexes studied, [Au(2)Cl(2)(micro-xantphos)], exhibiting luminescence thermochromism.

Opacity in the upper atmosphere of AU Mic

In this paper we investigate the validity of the optically thin assumption in the transition region of the late-type star AU Mic. We use Far-Ultraviolet Spectroscopic Explorer (FUSE) observations of the C III multiplet and O VI resonance lines, hence yielding information at two different levels within the atmosphere. Significant deviations from the optically thin fluxes are found for C III in both quiescent and flare spectra, where only 60% of the flux is actually observed. This could explain the apparent deviation of C III observed in emission measure distributions. We utilize escape probabilities for both homogeneous and inhomogeneous geometries and calculate optical depths as high as 10 for the C III 1175.71 Angstrom component of the multiplet. Using a lower limit to the electron density (10(11) cm(-3))we derive an effective thickness of

Thickness-induced stabilization of ferroelectricity in SrRuO3/Ba0.5Sr0.5TiO3/Au thin film capacitors

Pulsed-laser deposition has been used to fabricate Au/Ba0.5Sr0.5TiO3/SrRuO3/MgO thin film capacitor structures. Crystallographic and microstructural investigations indicated that the Ba0.5Sr0.5TiO3 (BST) had grown epitaxially onto the SrRuO3 lower electrode, inducing in-plane compressive and out- of-plane tensile strain in the BST. The magnitude of strain developed increased systematically as film thickness decreased. At room temperature this composition of BST is paraelectric in bulk. However, polarization measurements suggested that strain had stabilized the ferroelectric state, and that the decrease in film thickness caused an increase in remanent polarization. An increase in the paraelectric-ferroelectric transition temperature upon a decrease in thickness was confirmed by dielectric measurements. Polarization loops were fitted to Landau-Ginzburg-Devonshire (LGD) polynomial expansion, from which a second order paraelectric-ferroelectric transition in the films was suggested at a thickness of similar to500 nm. Further, the LGD analysis showed that the observed changes in room temperature polarization were entirely consistent with strain coupling in the system. (C) 2002 American Institute of Physics.

Measurement and interpretation of the mid-infrared properties of single crystal and polycrystalline gold

The contribution of electron-phonon scattering and grain boundary scattering to the mid-IR (lambda = 3.392 mum) properties of An has been assessed by examining both bulk, single crystal samples-Au(1 1 1) and Au(1 1 0)-and thin film, polycrystalline An samples at 300 K and 100 K by means of surface plasmon polariton excitation. The investigation constitutes a stringent test for the in-vacuo Otto-configuration prism coupler used to perform the measurements, illustrating its strengths and limitations. Analysis of the optical response is guided by a physically based interpretation of the Drude model. Relative to the reference case of single crystal Au at 100 K (epsilon = - 568 + i17.5), raising the temperature to 300 K causes increased electron-phonon scattering that accounts for a reduction of similar to40 nm in the electron mean free path. Comparison of a polycrystalline sample to the reference case determines a mean free path due to grain boundary scattering of similar to 17 nm, corresponding to about half the mean grain size as determined from atomic force microscopy and indicating a high reflectance coefficient for the An grain boundaries. An analysis combining consideration of grain boundary scattering and the inclusion of a small percentage of voids in the polycrystalline film by means of an effective medium model indicates a value for the grain boundary reflection coefficient in the range 0.55-0.71. (C) 2005 Elsevier B.V. All rights reserved.

Light emission from scanning tunnelling microscope on polycrystalline Au films - what is happening at the single-grain level?

When operated with a metallic tip and sample the scanning tunnelling microscope constitutes a nanoscale, plasmonic light source yielding broadband emission up to a photon energy determined by the applied bias. The emission is due to tunnelling electron excitation and subsequent radiative decay of localized plasmon modes, which can be on the lateral scale of a single metal grain (similar to 25 nm) or less. For a Au-tip/Au-polycrystalline sample under ambient conditions it is found that the intensity and spectral content of the emitted light are not dependent on the lateral grain dimension, but are predominantly determined by the tip geometry. However, the intensity increases strongly with increasing film thickness (grain depth) up to 20-25 nm or approximately the skin depth of the Au film. Photon maps can show less emissive grains and two classes of this occurrence are distinguished. The first is geometrical in origin - a double-tip structure in this case - while the second is due to a contamination-induced lowering of the local work function that causes the tunnel gap to increase. It is suggested that differences in work-function lowering between grains presenting different crystalline facets, combined with an exponential decay in emitted light intensity with tip - sample distance, leads to grain contrast. These results are relevant to tip-enhanced Raman scattering and the fabrication of micro/nano-scale planar, light-emitting tunnel devices.

Investigation of dead-layer thickness in SrRuO3/Ba0.5Sr0.5TiO3/Au thin-film capacitors

Thin-film capacitors, with barium strontium titanate (BST) dielectric layers between 7.5 and 950 nm in thickness, were fabricated by pulsed-laser deposition. Both crystallography and cation chemistry were consistent with successful growth of the BST perovskite. At room temperature, all capacitors displayed frequency dispersion such that epsilon (100 kHz)/epsilon (100 Hz) was greater than 0.75. The dielectric constant as a function of thickness was fitted, using the series capacitor model, for BST thicknesses greater than 70 nm. This yielded a large interfacial d(i)/epsilon (i) ratio of 0.40 +/-0.05 nm, implying a highly visible parasitic dead layer within the capacitor structure. Modeled consideration of the dielectric behavior for BST films, whose total thickness was below that of the dead layer, predicted anomalies in the plots of d/epsilon against d at the dead-layer thickness. In the capacitors studied here, no anomaly was observed. Hence, either (i) 7.5 nm is an upper limit for the total dead-layer thickness in the SRO/BST/Au system, or (ii) dielectric collapse is not associated with a distinct interfacial dead layer, and is instead due to a through-film effect. (C) 2001 American Institute of Physics.

Dynamic, in situ optical, magnetic and magneto-optical monitoring of the growth of Co/Au and Pd/Co/Au multilayer systems

The growth of magnetron sputtered Co/Au and Pd/Co/Au superlattices on Au and Pd buffer layers, deposited onto glass substrates, has been monitored optically and magneto-optically in real time, using rotating analyser ellipsometry and Kerr polarimetry, at a wavelength of 633 nm. The magneto-optical traces, combined with ex situ and in situ hysteresis loops, provide a detailed and informative fingerprint of the optical and magnetic properties of the films as they evolve during growth. For Co/Au, oscillations in the polar magneto-optical effect developed during the deposition of An overlayers on Co and these may be attributed to quantum well states. However, the hysteresis measurements show that the magnetic field required to maintain saturation magnetization throughout the experiment was larger than available in situ, introducing a degree of confusion concerning the interpretation of the data. This problem was overcome by the incorporation of Pd layers into the Co/Au structure, thereby eliminating variation in magnetic orientation during growth of the Au layers as a contributory factor to the observations.

An isothermal-isobaric Langevin thermostat for simulating nanoparticles under pressure: Application to Au clusters

We present a method for simulating clusters or, molecules subjected to an external pressure, which is exerted by a pressure-transmitting medium. It is based on the canoninical Langevin thermostat, but extended in such a way that the Brownian forces are allowed to operate only from the region exterior to the cluster. We show that the frictional force of the Langevin thermostat is linked to the pressure of the reservoir in a unique way, and that this property manifests itself when the particle it acts upon is not pointlike but has finite dimensions. By choosing appropriately the strength of the random forces and the friction coefficient, both temperature and pressure can be controlled independently. We illustrate the capabilities of this new method by calculating the compressibility of small gold clusters under pressure.

Catalytic Role of Metal Oxides in Gold-Based Catalysts: A First Principles Study of CO Oxidation on TiO2 Supported Au

CO oxidation on TiO2 supported Au has been studied using density functional theory calculations. Important catalytic roles of the oxide have been identified: (i) CO oxidation occurs at the interface between Au and the oxide with a very small barrier; and (ii) O-2 adsorption at the interface is the key step in the reaction. The physical origin of the oxide promotion effect has been further investigated: The oxide enhances electron transfer from the Au to the antibonding states of O-2, giving rise to (i) strong ionic bonding between the adsorbed O-2, Au, and the Ti cation; and (ii) a significant activation of O-2 towards CO oxidation.

Monte Carlo simulation of properties of monolayers and metal islands adsorbed on metallic (111) surfaces

To obtain the surface stress changes due to the adsorption of metal monolayers onto metallic surfaces, a new model derived from thermodynamic considerations is presented. Such a model is based on continuum Monte Carlo simulations with embedded atom method potentials in the canonical ensemble, and it is extended to consider the behavior on different islands adsorbed onto (111) substrate surfaces. Homoepitaxial and heteroepitaxial systems are studied. Pseudomorphic growth is not observed for small metal islands with considerable positive misfit with the substrate. Instead, the islands become compressed upon increase of their size. A simple model is proposed to interpolate between the misfits of atoms in small islands and the pseudomorphic behavior of the monolayer.

2D-drop model applied to the calculation of step formation energies on a (111) substrate

A model is presented for obtaining the step formation energy for metallic islands on (1 1 1) surfaces from Monte Carlo simulations. This model is applied to homo (Cu/Cu(1 1 1), Ag/Ag(1 1 1)) and heteroepitaxy (Ag/Pt(1 1 1)) systems. The embedded atom method is used to represent the interaction between the particles of the system, but any other type of potential could be used as well. The formulation can also be employed to consider the case of other single crystal surfaces, since the higher barriers for atom motion on other surfaces are not a hindrance for the simulation scheme proposed.

Quantitative analysis of the reactivity of formate species seen by DRIFTS over a Au/Ce(La)O2 water–gas shift catalyst: First unambiguous evidence of the minority role of formates as reaction intermediates

The reactivity of the species formed at the surface of a Au/Ce(La)O2 catalyst during the water������¢���¯���¿���½���¯���¿���½gas shift (WGS) reaction were investigated by operando diffuse reflectance Fourier transform spectroscopy (DRIFTS) at the chemical steady state during isotopic transient kinetic analyses (SSITKA). The exchanges of the reaction product CO2 and of formate and carbonate surface species were followed during an isotopic exchange of the reactant CO using a DRIFTS cell as a single reactor. The DRIFTS cell was a modified commercial cell that yielded identical reaction rates to that measured over a quartz plug-flow reactor. The DRIFTS signal was used to quantify the relative oncentrations of the surface species and CO2. The analysis of the formate exchange curves between 428 and 493 K showed that at least two levels of reactivity were present. ������¢���¯���¿���½���¯���¿���½Slow formates������¢���¯���¿���½���¯���¿���½ displayed an exchange rate constant 10- to 20-fold slower than that of the reaction product CO2. ������¢���¯���¿���½���¯���¿���½Fast formates������¢���¯���¿���½���¯���¿���½ were exchanged on a time scale similar to that of CO2. Multiple nonreactive readsorption of CO2 took place, accounting for the kinetics of the exchange of CO2(g) and making it impossible to determine the number of active sites through the SSITKA technique. The concentration (in mol g������¢���¯���¿���½���¯���¿���½1) of formates on the catalyst was determined through a calibration curve and allowed calculation of the specific rate of formate decomposition. The rate of CO2 formation was more than an order of magnitude higher than the rate of decomposition of formates (slow + fast species), indicating that all of the formates detected by DRIFTS could not be the main reaction intermediates in the production of CO2. This work stresses the importance of full quantitative analyses (measuring both rate constants and adsorbate concentrations) when investigating the role of adsorbates as potential reaction intermediates, and illustrates how even reactive species seen by DRIFTS may be unimportant in the overall reaction scheme.