Three-site model for hydrogen adsorption on supported platinum particles: influence of support ionicity and particle size on the hydrogen coverage

Pt L(3) X-ray absorption edge data on small supported Pt particles (N < 6.5) reveals that at very low H(2) pressure or high temperature the strongest bonded H is chemisorbed in an atop position. With decreasing temperature or at higher H(2) pressure only n-fold (n = 2 or 3) sites are occupied. At high H(2) pressure or low temperature, the weakest bonded H is positioned in an "ontop" site, with the chemisorbing Pt already having a stronger bond to a H atom in an n-fold site. DFT calculations show that the adsorption energy of hydrogen increases for Pt particles on ionic (basic) supports. The combination of the DFT calculations with hydrogen chemisorption data and the analysis of the Pt L(3) X-ray absorption spectra implies that both the H coverage and/or the type of active Pt surface sites, which are present at high temperature catalytic reaction conditions, strongly depend on the ionicity of the support. The consequences for Pt catalyzed hydrogenolysis and hydrogenation reactions will be discussed.     

Density functional calculation of the electronic absorption spectrum of Cu+ and Ag+ aqua ions

The UV absorption of aqueous Cu+ and Ag+ has been studied using Time Dependent Density Functional Theory (TDDFT) response techniques. The TDDFT electronic spectrum was computed from finite temperature dynamical trajectories in solution generated using the Density Functional Theory (DFT) based Ab Initio Molecular Dynamics (AIMD) method. The absorption of the two ions is shown to arise from similar excitation mechanisms, namely transitions from d orbitals localized on the metal center to a rather delocalized state originating from hybridization of the metal s orbital to the conduction band edge of the solvent. The ions differ in the way the spectral profile builds up as a consequence of solvent thermal motion. The Cu+ absorption is widely modulated, both in transition energies and intensities by fluctuations in the coordination environment which is characterized by the formation of strong coordination bonds to two water molecules in an approximately linear geometry. Though, on average, absorption intensities are typical of symmetry forbidden transitions of metal ions in the solid state, occasionally very short (<100 fs) bursts in intensity are observed, associated with anomalous Cu-H interactions. Absorption by the Ag+ complex is in comparison relatively stable in time, and can be interpreted in terms of the energy splitting of the metal 4d manifold in an average crystal field corresponding to a fourfold coordination in a distorted tetrahedral arrangement. Whereas the spectral profile of the Ag+ aqua ion is in good agreement with experiment, the overall position of the band is underestimated by 2 eV in the BLYP approximation to DFT. The discrepancy with experiment is reduced to 1.3 eV when a hybrid functional (PBE0) is used. The remaining inaccuracy of TDDFT in this situation is related to the delocalized character of the target state in d-->s transitions.     

Kinetic Study of the Copolymerisation of Ethylene with a Single Site Catalyst in Propane Slurry Polymerisation

Summary: The kinetic behaviour of a supported metallocene catalyst in slurry polymerisation of ethylene with 1-hexene under industrially relevant reaction conditions has been studied. Polymerisation experiments were carried out in a 5-litre stirred tank reactor in a temperature range from 60 to 80 °C and ethylene partial pressures from 5 to 15 bar. Comonomer and hydrogen amounts were varied as well. The catalyst showed pronounced activation and slow deactivation during runtimes of about 1 hour. Strong influences of 1-hexene (“hexene effect”) and hydrogen (“hydrogen effect”) on the activity profiles were observed. Based on the experimental results, a kinetic model has been derived in order to describe and predict important polymerisation data such as activity profile, comonomer content and molecular weight distributions with respect to the reaction conditions. The presented kinetic model is able to describe the observed effects of 1-hexene and hydrogen on the activity profiles, as well as the comonomer incorporation across a broad range of polymerisation conditions. The molecular weight distributions can be simulated with good qualitative agreement to the experimental data.     

A Versatile Approach to CF3‐Containing 2‐Pyrrolidones by Tandem Michael Addition–Cyclization: Exemplification in the Synthesis of Amidine Class BACE1 Inhibitors

The synthesis of new fluorinated pyrrolidones starting from unprotected amino esters and amino nitriles through a Michael addition–lactamization sequence is described. The resulting CF₃‐containing building blocks, bearing a quaternary stereogenic center adjacent to the fluorinated group, have been converted into amino pyrrolidines that display potent β‐secretase 1 (BACE1) inhibitory activity. This work constitutes an example of selective fluorination as a valid strategy for the modulation of physicochemical and biological properties of lead compounds in drug discovery.     

X-ray microtomography for studying localized deformation in fine-grained geomaterials under triaxial compressionUtilisation de la microtomographie rayon X pour l'étude de la localisation des déformations dans les géomatériaux argileux sous sollicitation axisymétrique.

This Note presents a few selected results of an experimental testing program carried out at the ESRF in Grenoble, France. X-ray microtomography (with a spatial resolution of 14 μm) has been used to evaluate the onset and evolution of shear banding in a fine-grained stiff soil under deviatoric loading. It allowed detailed observations of strain localization in a specimen during the test, including the presence of more than one shear zone and a varying degree of dilatancy and/or crack opening. To cite this article: G. Viggiani et al., C. R. Mecanique 332 (2004).     

Stacking in sediments of colloidal hard spheres

We use computer simulations to investigate the crystallization dynamics of sedimenting hard spheres in large systems (hundreds of thousands of particles). We show that slow sedimentation results primarily in face-centered cubic (fcc) stacked crystals, instead of random hexagonal close packed or hexagonal close packed (hcp) crystals. We also find slanted stacking faults, in the fcc regions. However, we attribute the formation of fcc to the free energy difference between fcc and hcp and not to the presence of these slanted stacking faults. Although the free energy difference between hcp and fcc per particle is small (only 10(-3) times the thermal energy), it can become considerable, when multiplied by the number of particles in each domain. The ratio of fcc to hcp obtained from dynamic simulations is in excellent agreement with well-equilibrated Monte Carlo simulations, in which no slanted stacking faults were found. Our results explain a range of experiments on colloids, in which the amount of fcc increases upon lowering the sedimentation rate or decreasing the initial volume fraction.     

Gelatin‐Methacrylamide Hydrogels as Potential Biomaterials for Fabrication of Tissue‐Engineered Cartilage Constructs

Gelatin‐methacrylamide (gelMA) hydrogels are shown to support chondrocyte viability and differentiation and give wide ranging mechanical properties depending on several cross‐linking parameters. Polymer concentration, UV exposure time, and thermal gelation prior to UV exposure allow for control over hydrogel stiffness and swelling properties. GelMA solutions have a low viscosity at 37 °C, which is incompatible with most biofabrication approaches. However, incorporation of hyaluronic acid (HA) and/or co‐deposition with thermoplastics allows gelMA to be used in biofabrication processes. These attributes may allow engineered constructs to match the natural functional variations in cartilage mechanical and geometrical properties.

     

Computing the Detour and Spanning Ratio of Paths, Trees, and Cycles in 2D and 3D

The detour and spanning ratio of a graph G embedded in measure how well G approximates Euclidean space and the complete Euclidean graph, respectively. In this paper we describe O(nlog n) time algorithms for computing the detour and spanning ratio of a planar polygonal path. By generalizing these algorithms, we obtain O(nlog ² n)-time algorithms for computing the detour or spanning ratio of planar trees and cycles. Finally, we develop subquadratic algorithms for computing the detour and spanning ratio for paths, cycles, and trees embedded in , and show that computing the detour in is at least as hard as Hopcroft’s problem. This research was partly funded by CRM, FCAR, MITACS, and NSERC. P.A. was supported by NSF under grants CCR-00-86013 EIA-99-72879, EIA-01-31905, and CCR-02-04118, by ARO grants W911NF-04-1-0278 and DAAD19-03-1-0352, and by a grant from the U.S.-Israeli Binational Science Foundation. R.K. was supported by DFG grant Kl 655/14-1. M.S. was supported by NSF Grants CCR-97-32101 and CCR-00-98246, by a grant from the U.S.-Israeli Binational Science Foundation (jointly with P.A.), by a grant from the Israeli Academy of Sciences for a Center of Excellence in Geometric Computing at Tel Aviv University, and by the Hermann Minkowski–MINERVA Center for Geometry at Tel Aviv University. Some of these results have appeared in a preliminary form in [2, 20].     

A classical point charge model study of system size dependence of oxidation and reorganization free energies in aqueous solution

The response of water to a change of charge of a solvated ion is, to a good approximation, linear for the type of iron-like ions frequently used as a model system in classical force field studies of electron transfer. Free energies for such systems can be directly calculated from average vertical energy gaps. Exploiting this feature, we have computed the free energy and the reorganization energy of the M2+/M3+ and M1+/M2+ oxidations in a series of model systems all containing a single Mn+ ion and an increasing number of simple point charge water molecules. Long-range interactions are taken into account by Ewald summation methods. Our calculations confirm the observation made by Hummer, Pratt, and Garcia (J. Phys. Chem. 1996, 100, 1206) that the finite size correction to the estimate of solvation energy (and hence oxidation free energy) in such a setup is effectively proportional to the inverse third power (1/L3) of the length L of the periodic cell. The finite size correction to the reorganization energy is found to scale with 1/L. These simulation results are analyzed using a periodic generalization of the Born cavity model for solvation, yielding three different estimates of the cavity radius, namely, from the infinite system size extrapolation of oxidation free energy and reorganization energy, and from the slope of the linear dependence of oxidation free energy on 1/L3. The cavity radius for the reorganization energy is found to be significantly larger compared to the radius for the oxidation (solvation) free energy. The radius controlling the 1/L3 dependence of oxidation free energy is found to be comparable to the radius for reorganization. The implication of these results for density functional theory-based ab initio molecular dynamics calculation of redox potentials is discussed.