Nature of Ar bonding to small Co_n^+ clusters and its effect on the structure determination by far-infrared absorption spectroscopy

Far-infrared vibrational spectroscopy by multiple photon dissociation has proven to be a very useful technique for the structural fingerprinting of small metal clusters. Contrary to previous studies on cationic V, Nb and Ta clusters, measured vibrational spectra of small cationic cobalt clusters show a strong dependence on the number of adsorbed Ar probe atoms, which increases with decreasing cluster size. Focusing on the series Co_4^+ to Co_8^+ we therefore use density-functional theory to analyze the nature of the Ar-Co_n^+ bond and its role for the vibrational spectra. In a first step, energetically low-lying isomer structures are identified through first-principles basin-hopping sampling runs and their vibrational spectra computed for a varying number of adsorbed Ar atoms. A comparison of these fingerprints with the experimental data enables in some cases a unique assignment of the cluster structure. Independent of the specific low-lying isomer, we obtain a pronounced increase of the Ar binding energy for the smallest cluster sizes, which correlates nicely with the observed increased influence of the Ar probe atoms on the IR spectra. Further analysis of the electronic structure motivates a simple electrostatic picture that not only explains this binding energy trend, but also why the influence of the rare-gas atom is much stronger than in the previously studied systems.Comment: 12 pages including 10 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm

Comparative analysis of suspended sand concentration recorded with different techniques in a rippled bed regime

Sediment entrainment processes due to the oscillatory flow above rippled and plane sea beds are fundamentally different. Whereas above plane beds the sheet flow or bed load regime dominates and the momentum transfer is primarily caused by turbulent diffusion, above a sea bed covered with long crested vortex ripples the well organised coherent vortex mechanisms induce sediment-laden lee vortices at the ripple crest, which will be detached from the bed ejected into the water column and finally shed when the flow reverses. To investigate the sediment entrainment processes above vortex ripples, a study was carried out in the Large Wave Flume (GWK) aiming firstly to find out the most appropriate measuring technique to determine the suspended sediment concentration both temporarily and spatially. and secondly to analyse the intra-wave sediment entrainment processes around a steep ripple.EC/FP6/SANDSBMBF/ModPr

The magic triangle goes MAD: experimental phasing with a bromine derivative

5-Amino-2,4,6-tribromoisophthalic acid is used as a phasing tool for protein structure determination by MAD phasing. It is the second representative of a novel class of compounds for heavy-atom derivatization that combine heavy atoms with amino and carboxyl groups for binding to proteins

Distribution and Fluctuation of Firm Size in the Long-Run

The paper studies empirically and analytically growth and fluctuation of firm size distribution. An empirical analysis is carried out on several data sets on firm size, with emphasis on one-time distribution as well as growth-rate probability distribution. Two well-known scaling laws, Pareto's law and Gibrat's law, are discussed. Some theoretical discussion on their relationship is presented. We also discuss to what extent there may exist economic mechanisms that produce an unequal firm size distribution in the long run. The mechanisms we study have been known in the economic literature since long. Yet, they have not been studied in the context of a dynamic decision problem of the firm. We allow for heterogeneity of firms with respect to certain characteristics. We then show that there are mechanisms at work which may generate a twin-peaked distribution of firm size in the long-run, which will then be tested empiricallyFirm size, Pareto's law, Gibrat's law

Stabilization of controlled diffusions via Zubov's method

We consider a controlled stochastic system which is exponentially stabilizable in probability near an attractor. Our aim is to characterize the set of points which can be driven by a suitable control to the attractor with either positive probability or with probability one. This will be done by associating to the stochastic system a suitable control problem and the corresponding Zubov equation. We then show that this approach can be used as a basis for numerical computations of these sets

Dispensing pico to nanolitre of a natural hydrogel by laser-assisted bioprinting

<p>Abstract</p> <p>Background</p> <p>Laser-assisted bioprinting of multi-cellular replicates in accordance with CAD blueprint may substantially improve our understandings of fundamental aspects of 3 D cell-cell and cell-matrix interactions <it>in vitro</it>. For predictable printing results, a profound knowledge about effects of different processing parameters is essential for realisation of 3 D cell models with well-defined cell densities.</p> <p>Methods</p> <p>Time-resolved imaging of the hydrogel jet dynamics and quantitative assessment of the dependence of printed droplet diameter on the process characteristics were conducted.</p> <p>Results</p> <p>The existence of a counterjet was visualised, proving the bubble collapsing theory for the jet formation. Furthermore, by adjusting the viscosity and height of the applied hydrogel layer in combination with different laser pulse energies, the printing of volumes in the range of 10 to 7000 picolitres was demonstrated. Additionally, the relationship between the viscosity and the layer thickness at different laser pulse energies on the printed droplet volume was identified.</p> <p>Conclusions</p> <p>These findings are essential for the advancement of laser-assisted bioprinting by enabling predictable printing results and the integration of computational methods in the generation of 3 D multi-cellular constructs.</p

Role of dispersion of vanadia on SBA-15 in the oxidative dehydrogenation of propane

A series of vanadia catalysts supported on the mesoporous silica SBA-15 are synthesized using an automated laboratory reactor. The catalysts contain from 0.6 up to 13.6V atoms/nm2 and are structurally characterized by various techniques (BET, XRD, SEM, TEM, Raman, IR, UV/Vis). Samples containing up to 3.1V/nm2 are structurally rather similar. They all contain a mixture of tetrahedral (VOx)n species, both monomeric and oligomeric. The ratio of monomeric and oligomeric species depends on the vanadia loading. At the highest loading of 13.6V/nm2, in addition to tetrahedral (VOx)n, also substantial amounts of three-dimensional, bulk-like V2O5 are present in the catalyst. The structural similarity of the low-loaded catalysts is reflected in their alike catalytical activity during the oxidative dehydrogenation (ODH) of propane between 380 and 480 °C. Propene, CO, and CO2 are formed as reaction products, while neither the formation of ethene nor acrolein or acrylic acid is observed in other than trace amounts. The activation energy for ODH of propane is not, vert, similar140 kJ/mol. The catalyst with the highest loading yields varying activation energies for different reaction conditions, which is probably related to rearrangements between bulk-like and dispersed, two-dimensional (VOx)n. Rather than the monomer to oligomer ratio, the ratio of two-dimensional to three-dimensional vanadia seems to be crucial for the catalytic properties of silica supported vanadia in the ODH of propane