The surface geometry of carbonmonoxide and hydrogen co-adsorbed on Ni 111

A combination of photoelectron spectroscopy, temperature programmed desorption and low energy electron diffraction structure determinations have been applied to study the p(2 x 2) structures of pure hydrogen and co-adsorbed hydrogen and CO on Ni {111}. In agreement with earlier work atomic hydrogen is found to adsorb on fcc and hcp sites in the pure layer with H-Ni bond lengths of 1.74Angstrom. The substrate interlayer distances, d(12) = 2.05Angstrom and d(23) = 2.06Angstrom, are expanded with respect to clean Ni {111} with buckling of 0.04Angstrom in the first layer. In the co-adsorbed phase Co occupies hcp sites and only the hydrogen atoms on fcc sites remain on the surface. d(12) is even further expanded to 2.08Angstrom with buckling in the first and second layer of 0.06 and 0.02Angstrom, respectively. The C-O, C-Ni, and H-Ni bond lengths are within the range of values also found for the pure adsorbates.

The interplay between geometry, electronic structure, and reactivity of Cu-Ni bimetallic (111) surfaces

The mutual influence of surface geometry (e.g. lattice parameters, morphology) and electronic structure is discussed for Cu-Ni bimetallic (111) surfaces. It is found that on flat surfaces the electronic d-states of the adlayer experience very little influence from the substrate electronic structure which is due to their large separation in binding energies and the close match of Cu and Ni lattice constants. Using carbon monoxide and benzene as probe molecules, it is found that in most cases the reactivity of Cu or Ni adlayers is very similar to the corresponding (111) single crystal surfaces. Exceptions are the adsorption of CO on submonolayers of Cu on Ni(111) and the dissociation of benzene on Ni/Cu(111) which is very different from Ni(111). These differences are related to geometric factors influencing the adsorption on these surfaces.

Adsorption and dissociation of benzene on bimetallic surfaces - the influence of surface geometry and electronic structure

This topical review discusses the influence of the surface geometry (e.g. lattice parameters and termination) and electronic structure of well-defined bimetallic surfaces on the adsorption and dissociation of benzene. The available data can be divided into two categories with combinations of non-transition metals and transition metals on the one side and combinations of two transition metals on the other. The main effect of non-transition metals in surface alloys is site blocking which can suppress chemisorption and dissociation of the molecules completely. When two transition metals are combined, the effects are less dramatic. They mainly affect the strength of the chemisorption bond and the degree of dissociation due to electronic and template effects.

The surface geometry of carbon monoxide and oxygen co-adsorbed on Ni{111}

Low energy electron diffraction (LEED) structure determinations have been performed for the p(2 x 2) structures of pure oxygen and oxygen co-adsorbed with CO on Ni{111}. Optimisation of the non-geometric parameters led to very good agreement between experimental and theoretical IV-curves and hence to a high accuracy in the structural parameters. In agreement with earlier work atomic oxygen is found to adsorb on fee sites in both structures. In the co-adsorbed phase CO occupies atop sites. The positions of the substrate atoms are almost identical, within 0.02 Angstrom, in both structures, implying that the interaction with oxygen dominates the arrangement of Ni atoms at the surface.

Electronic transitions and bonding properties in a series of five-coordinate “16-electron” complexes [Mn(CO)3(L2)]− (L2=chelating redox-active π-donor ligand)

In this article we present for the first time accurate density functional theory (DFT) and time-dependent (TD) DFT data for a series of electronically unsaturated five-coordinate complexes [Mn(CO)(3)(L-2)](-), where L-2 stands for a chelating strong pi-donor ligand represented by catecholate, dithiolate, amidothiolate, reduced alpha-diimine (1,4-dialkyl-1,4-diazabutadiene (R-DAB), 2,2'-bipyridine) and reduced 2,2'-biphosphinine types. The single-crystal X-ray structure of the unusual compound [Na(BPY)][Mn(CO)(3)(BPY)]center dot Et2O and the electronic absorption spectrum of the anion [Mn(CO)(3)(BPY)](-) are new in the literature. The nature of the bidentate ligand determines the bonding in the complexes, which varies between two limiting forms: from completely pi-delocalized diamagnetic {(CO)(3)Mn-L-2}(-) for L-2 = alpha-diimine or biphosphinine, to largely valence-trapped {(CO)(3)Mn-1-L-2(2-)}(-) for L-2(2-) = catecholate, where the formal oxidation states of Mn and L-2 can be assigned. The variable degree of the pi-delocalization in the Mn(L-2) chelate ring is indicated by experimental resonance Raman spectra of [Mn(CO)(3)(L-2)](-) (L-2=3,5-di-tBu-catecholate and iPr-DAB), where accurate assignments of the diagnostically important Raman bands have been aided by vibrational analysis. The L-2 = catecholate type of complexes is known to react with Lewis bases (CO substitution, formation of six-coordinate adducts) while the strongly pi-delocalized complexes are inert. The five-coordinate complexes adopt usually a distorted square pyramidal geometry in the solid state, even though transitions to a trigonal bipyramid are also not rare. The experimental structural data and the corresponding DFT-computed values of bond lengths and angles are in a very good agreement. TD-DFT calculations of electronic absorption spectra of the studied Mn complexes and the strongly pi-delocalized reference compound [Fe(CO)(3)(Me-DAB)] have reproduced qualitatively well the experimental spectra. Analyses of the computed electronic transitions in the visible spectroscopic region show that the lowest-energy absorption band always contains a dominant (in some cases almost exclusive) contribution from a pi(HOMO) -> pi*(LUMO) transition within the MnL2 metallacycle. The character of this optical excitation depends strongly on the composition of the frontier orbitals, varying from a partial L-2 -> Mn charge transfer (LMCT) through a fully delocalized pi(MnL2) -> pi*(MnL2) situation to a mixed (CO)Mn -> L-2 charge transfer (LLCT/MLCT). The latter character is most apparent in the case of the reference complex [Fe(CO)(3)(Me-DAB)]. The higher-lying, usually strongly mixed electronic transitions in the visible absorption region originate in the three lower-lying occupied orbitals, HOMO - 1 to HOMO - 3, with significant metal-d contributions. Assignment of these optical excitations to electronic transitions of a specific type is difficult. A partial LLCT/MLCT character is encountered most frequently. The electronic absorption spectra become more complex when the chelating ligand L-2, such as 2,2'-bipyridine, features two or more closely spaced low-lying empty pi* orbitals.

Integrating features for man-made target tracking from FLIR image sequence using particle filter

A new man-made target tracking algorithm integrating features from (Forward Looking InfraRed) image sequence is presented based on particle filter. Firstly, a multiscale fractal feature is used to enhance targets in FLIR images. Secondly, the gray space feature is defined by Bhattacharyya distance between intensity histograms of the reference target and a sample target from MFF (Multi-scale Fractal Feature) image. Thirdly, the motion feature is obtained by differencing between two MFF images. Fourthly, a fusion coefficient can be automatically obtained by online feature selection method for features integrating based on fuzzy logic. Finally, a particle filtering framework is developed to fulfill the target tracking. Experimental results have shown that the proposed algorithm can accurately track weak or small man-made target in FLIR images with complicated background. The algorithm is effective, robust and satisfied to real time tracking.

The adsorption geometry and chemical state of lysine on Cu{110}

Chemisorbed layers of lysine adsorbed on Cu{110} have been studied using X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. XPS indicates that the majority (70%) of the molecules in the saturated layer at room temperature (coverage 0.27 ML) are in their zwitterionic state with no preferential molecular orientation. After annealing to 420 K a less densely packed layer is formed (0.14 ML), which shows a strong angular dependence in the characteristic π-resonance of oxygen K edge NEXAFS and no indication of zwitterions in XPS. These experimental results are best compatible with molecules bound to the substrate through the oxygen atoms of the (deprotonated) carboxylate group and the two amino groups involving Cu atoms in three different close packed rows. This μ4 bonding arrangement with an additional bond through the !-amino group is different from geometries previously suggested for lysine on Cu{110}.

Surface based hypothesis verification in intensity images using geometric and appearance data

In this paper we discuss current work concerning Appearance-based and CAD-based vision; two opposing vision strategies. CAD-based vision is geometry based, reliant on having complete object centred models. Appearance-based vision builds view dependent models from training images. Existing CAD-based vision systems that work with intensity images have all used one and zero dimensional features, for example lines, arcs, points and corners. We describe a system we have developed for combining these two strategies. Geometric models are extracted from a commercial CAD library of industry standard parts. Surface appearance characteristics are then learnt automatically by observing actual object instances. This information is combined with geometric information and is used in hypothesis evaluation. This augmented description improves the systems robustness to texture, specularities and other artifacts which are hard to model with geometry alone, whilst maintaining the advantages of a geometric description.