Solving surface structures from normal incidence X-ray standing wave data

A program is provided to determine structural parameters of atoms in or adsorbed on surfaces by refinement of atomistic models towards experimentally determined data generated by the normal incidence X-ray standing wave (NIXSW) technique. The method employs a combination of Differential Evolution Genetic Algorithms and Steepest Descent Line Minimisations to provide a fast, reliable and user friendly tool for experimentalists to interpret complex multidimensional NIXSW data sets

Spectroscopy of ultrathin epitaxial rutile TiO[sub 2](110) films grown on W(100)

Epitaxial ultrathin titanium dioxide films of 0.3 to similar to 7 nm thickness on a metal single crystal substrate have been investigated by high resolution vibrational and electron spectroscopies. The data complement previous morphological data provided by scanned probe microscopy and low energy electron diffraction to provide very complete characterization of this system. The thicker films display electronic structure consistent with a stoichiometric TiO2 phase. The thinner films appear nonstoichiometric due to band bending and charge transfer from the metal substrate, while work function measurements also show a marked thickness dependence. The vibrational spectroscopy shows three clear phonon bands at 368, 438, and 829 cm(-1) (at 273 K), which confirms a rutile structure. The phonon band intensity scales linearly with film thickness and shift slightly to lower frequencies with increasing temperature, in accord with results for single crystals. (c) 2007 American Institute of Physics

Adsorption of organic molecules at the TiO2(110) surface: the effect of van der Waals interactions

Understanding the interaction of organic molecules with TiO2 surfaces is important for a wide range of technological applications. While density functional theory (DFT) calculations can provide valuable insight about these interactions, traditional DFT approaches with local exchange-correlation functionals suffer from a poor description of non-bonding van der Waals (vdW) interactions. We examine here the contribution of vdW forces to the interaction of small organic molecules (methane, methanol, formic acid and glycine) with the TiO2 (110) surface, based on DFT calculations with the optB88-vdW functional. The adsorption geometries and energies at different configurations were also obtained in the standard generalized gradient approximation (GGA-PBE) for comparison. We find that the optB88-vdW consistently gives shorter surface adsorbate-to-surface distances and slightly stronger interactions than PBE for the weak (physisorbed) modes of adsorption. In the case of strongly adsorbed (chemisorbed) molecules both functionals give similar results for the adsorption geometries, and also similar values of the relative energies between different chemisorption modes for each molecule. In particular both functionals predict that dissociative adsorption is more favourable than molecular adsorption for methanol, formic acid and glycine, in general agreement with experiment. The dissociation energies obtained from both functionals are also very similar, indicating that vdW interactions do not affect the thermodynamics of surface deprotonation. However, the optB88-vdW always predicts stronger adsorption than PBE. The comparison of the methanol adsorption energies with values obtained from a Redhead analysis of temperature programmed desorption data suggests that optB88-vdW significantly overestimates the adsorption strength, although we warn about the uncertainties involved in such comparisons.Comment: 32 pages, 8 figures; accepted in Surface Scienc

Structure of adsorbed organometallic rhodium: model single atom catalysts

We have determined the structure of a complex rhodium carbonyl chloride [Rh(CO)(2)Cl] molecule adsorbed on the TiO2 (110) surface by the normal incidence x-ray standing wave technique. The data show that the technique is applicable to reducible oxide systems and that the dominant adsorbed species is undissociated with Rh binding atop bridging oxygen and to the Cl found close to the fivefold coordinated Ti ions in the surface. A minority geminal dicarboryl species, where Rh-Cl bond scission has occurred, is found bridging the bridging oxygen ions forming a high-symmetry site

Variable Bias Coin Tossing

Alice is a charismatic quantum cryptographer who believes her parties are unmissable; Bob is a (relatively) glamorous string theorist who believes he is an indispensable guest. To prevent possibly traumatic collisions of self-perception and reality, their social code requires that decisions about invitation or acceptance be made via a cryptographically secure variable bias coin toss (VBCT). This generates a shared random bit by the toss of a coin whose bias is secretly chosen, within a stipulated range, by one of the parties; the other party learns only the random bit. Thus one party can secretly influence the outcome, while both can save face by blaming any negative decisions on bad luck. We describe here some cryptographic VBCT protocols whose security is guaranteed by quantum theory and the impossibility of superluminal signalling, setting our results in the context of a general discussion of secure two-party computation. We also briefly discuss other cryptographic applications of VBCT.Comment: 14 pages, minor correction

Structure and stress of Re(11%21); chiral terraces at a racemic surface

The surface structure and morphology of the clean Re(11%21) surface has been investigated through combined low energy electron diffraction intensity analysis of data taken at multiple angles of incidence, scanning tunneling microscopy, and first-principles density functional calculations. The results show how this globally racemic surface terminates in two chirally distinct terraces, which show largescale out-of-plane atomic relaxations and in-plane lateral movement of the uppermost atoms. We further identify and discuss the initial stages of step bunching upon adsorption of oxygen that leads ultimately to the large-scale faceting of the surface. Finally, we present calculations of surface stress and the response to applied surface strain, which suggest routes to the exertion of control over the expression of chirality at the surface

Copper deposition on TiO2 from copper(II)hexafluoroacetylacetonate

The authors have studied the adsorption of CuII(hfac)2 on the surface of a model oxide system, TiO2(110), and probed the molecular stability with respect to thermal cycling, using atomic scale imaging by scanning tunneling microscopy supported by x-ray photoemission spectroscopy. They find that at 473 K, the adsorbed metal-organic molecules begin to dissociate and release Cu atoms which aggregate and form Cu nanoparticles. These Cu nanoparticles ripen over time and the size (height) distribution develops into a bimodal distribution. Unlike other organometallic systems, which show a bimodal distribution due to enhanced nucleation or growth at surface step edges, the nanoparticles do not preferentially form at steps. The reduced mobility of the Cu islands may be related to the co-adsorbed ligands that remain in very small clusters on the surface

Oxidation of polycrystalline Ni studied by spectromicroscopy: Phase separation in the early stages of crystallite growth

Low-energy and photoemission electron microscopy enables the determination of facet planes of polycrystalline surfaces and the study of their chemical composition at the sub-m scale. Using these techniques the early oxidation stages of nickel were studied. After exposing the surface to 20 L of oxygen at 373 K a uniform layer of chemisorbed oxygen was found on all facets. After oxygen exposure at 473–673 K, small NiO crystallites are formed on all facets but not in the vicinity of all grain boundaries. The crystallites are separated by areas of bare Ni without significant oxygen coverage

A combined experimental and theoretical study of methyl acetoacetate adsorption on Ni{100}

The enantio-selective hydrogenation of methyl acetoacetate (MAA) over modified Ni-based catalysts is a key reaction in the understanding of enantioselective heterogeneous catalysis as it represents the only example of this class of reactions catalysed by base metals. Yet, there is very little molecular-level information available about the adsorption complex formed by the reactants on Ni surfaces. Here, we report a combined experimental and theoretical study of the adsorption of MAA on the Ni{100} surface. X-ray photoelectron spectroscopy shows that MAA forms stable multilayers at low temperatures, which desorb between 200 K and 220 K. At higher temperatures a single chemisorbed layer is formed, which decomposes between 300 K and 350 K. Density functional theory modelling predicts an enolate species with bidentate coordination as the most stable chemisorbed species. Comparison of photoelectron spectroscopy and X-ray absorption data with simulations using this adsorption model show good qualitative and quantitative agreement. The molecular plane is tilted with respect to the surface plane by about 50deg. This breaking of symmetry provides a mechanism for the enantio-selective hydrogenation

Application of diagnostic techniques to an experimental aircraft fuel rig

An important issue for Aerospace and Defence Systems providers is how to reduce the risks associated with installing a new Fault Detection Tool (FDT) on a system. It is highly desirable that some degree of assessment, selection and validation is carried out before the FDT is integrated with the system. This paper describes the initial phases of a project to investigate the processes behind the assessment and validation using an Experimental Aircraft Fuel Rig (referred to as the Advanced Diagnostic Test-bed ADT). This paper also presents results from preliminary verification and validation work that has been used on a mathematical model of the ADT, and also some results from some initial diagnostic technique assessment that has been performed using real experimental data from the ADT and simulated data from mathematical models