Understanding,Controlling and Programming Cooperativity in Self‐Assembled Polynuclear Complexes in Solution

Deviations from statistical binding, that is cooperativity, in self‐assembled polynuclear complexes partly result from intermetallic interactions ΔE^M,M, whose magnitudes in solution depend on a balance between electrostatic repulsion and solvation energies. These two factors have been reconciled in a simple point‐charge model, which suggests severe and counter‐intuitive deviations from predictions based solely on the Coulomb law when considering the variation of ΔE^M,M with metallic charge and intermetallic separation in linear polynuclear helicates. To demonstrate this intriguing behaviour, the ten microscopic interactions that define the thermodynamic formation constants of some twenty‐nine homometallic and heterometallic polynuclear triple‐stranded helicates obtained from the coordination of the segmental ligands L1 – L11 with Zn²⁺ (a spherical d‐block cation) and Lu³⁺ (a spherical 4f‐block cation), have been extracted by using the site binding model. As predicted, but in contrast with the simplistic coulombic approach, the apparent intramolecular intermetallic interactions in solution are found to be i) more repulsive at long distance ( > ), ii) of larger magnitude when Zn²⁺ replaces Lu³⁺ ( > ) and iii) attractive between two triply charged cations held at some specific distance ( <0). The consequences of these trends are discussed for the design of polynuclear complexes in solution.     

Blow up of solutions of the Cauchy problem for a wave equation with nonlinear damping and source terms and positive initial energy

In this paper we consider the long time behavior of solutions of the initial value problem for semi-linear wave equations of the form

Here 0.$">

We prove that if m \ge 1,$"> then for any 0$"> there are choices of initial data from the energy space with initial energy such that the solution blows up in finite time. If we replace by , where is a sufficiently slowly decreasing function, an analogous result holds.

     

Infrared spectroscopy study of adsorption and coadsorption of carbon monoxide and hydrogen on Ru/Al203

IR spectroscopy was used to study CO adsorption and coadsorption with H₂ on 5% Ru/Al₂O₃. By variation of sample pretreatment, CO pressures, contact time and temperature several surface species were identified: mono– and multicarbonyl species formed with ruthenium in different oxidation state and on various sites of the catalyst surface. During CO and H₂ coadsorption and interaction, a new band at 2030 cm^–1 was registered. It was assigned to a 'hydrocarbonyl' species on the metal particles. Thermal stability of some CO species was studied. Most stable and least reactive species was found to be a multicarbonyl giving rise to bands at 1980 and 2060 cm^–1.     

Ab initio study of S dynamics on iron surfaces

Density functional theory was employed to examine the interactions of atomic sulfur with the Fe(1 0 0) and Fe(1 1 0) surfaces. Vibrational frequency calculations were performed to determine the nature of stationary points at the high symmetry atop, bridge and hollow adsorption sites and to indicate the direction the adsorbate would move across the surface. The values were also used in the determination of the rate constant for hopping of S from one energy minimum site to another. Ab initio molecular dynamics (MD) simulations were then performed to monitor the mobility of the S atom on the (1 0 0) surface at different temperatures up to the melting point of Fe (1808 K) and were compared to our previously obtained ab initio MD results for S/Fe(1 1 0) [N. Todorova, M.J.S. Spencer, I. Yarovsky, Australian Institute of Physics 16th Biennial Congress, 2005, Canberra, Australia, ISBN 0-9598064-8-2].     

Role of subsurface oxygen in oxide formation at transition metal surfaces

We present a density-functional theory trend study addressing the incorporation of oxygen into the basal plane of the late 4d transition metals (TMs) from Ru to Ag. Occupation of subsurface sites is always connected with a significant distortion of the host lattice, rendering it initially less favorable than on-surface chemisorption. Penetration starts only after a critical coverage theta(c), which is lower for the softer metals towards the right of the TM series. The computed theta(c) are found to be very similar to those above which the bulk oxide phase becomes thermodynamically more stable, thus suggesting that the initial incorporation of O actuates the formation of a surface oxide on TM surfaces.