The Atomic Slide Puzzle: Self-Diffusion of an Impure Atom

In a series of recent papers van Gastel et al have presented first experimental evidence that impure, Indium atoms, embedded into the first layer of a Cu(001) surface, are not localized within the close-packed surface layers but make concerted, long excursions visualized in a series of STM images. Such excursions occur due to continuous reshuffling of the surface following the position exchanges of both impure and host atoms with the naturally occuring surface vacancies. Van Gastel et al have also formulated an original lattice-gas type model with asymmetric exchange probabilities, whose numerical solution is in a good agreement with the experimental data. In this paper we propose an exact lattice solution of several versions of this model.Comment: Latex, 4 pages, 2 figures, to appear in Phys. Rev. E (RC

Device, system and method for determining vital sign information of a subject

The present invention relates to a device, system and a method for determining vital sign information of a subject. To provide an increased signal quality and an improved robustness of the obtained vital sign information with respect to motion and low SNR, the proposed device tries to find the linear combination of the color channels, which suppresses the distortions best in a frequency band including the pulse rate, and consequently use this same linear combination to extract the desired vital sign information (e.g. represented by a vital sign information signal such as a respiration signal or Mayer waves) in a lower frequency band.</p

Nothing moves a surface: vacancy mediated surface diffusion

We report scanning tunneling microscopy observations, which imply that all atoms in a close-packed copper surface move frequently, even at room temperature. Using a low density of embedded indium `tracer' atoms, we visualize the diffusive motion of surface atoms. Surprisingly, the indium atoms seem to make concerted, long jumps. Responsible for this motion is an ultra-low density of surface vacancies, diffusing rapidly within the surface. This interpretation is supported by a detailed analysis of the displacement distribution of the indium atoms, which reveals a shape characteristic for the vacancy mediated diffusion mechanism that we propose.Comment: 4 pages; for associated movie, see http://www-lion.leidenuniv.nl/sections/cm/groups/interface/projects/therm

Converged Structural and Spectroscopic Properties for Refined QM/MM Models of Azurin

Blue copper proteins continue to challenge experiment and theory with their electronic structure and spectroscopic properties that respond sensitively to the coordination environment of the copper ion. In this work, we report state-of-the art electronic structure studies for geometric and spectroscopic properties of the archetypal “Type I” copper protein azurin in its Cu(II) state. A hybrid quantum mechanics/molecular mechanics (QM/MM) approach is used, employing both density functional theory (DFT) and coupled cluster with singles, doubles, and perturbative triples (CCSD(T)) methods for the QM region, the latter method making use of the domain-based local pair natural orbital (DLPNO) approach. Models of increasing QM size are employed to investigate the convergence of critical geometric parameters. It is shown that convergence is slow and that a large QM region is critical for reproducing the short experimental Cu–SCys112 distance. The study of structural convergence is followed by investigation of spectroscopic parameters using both DFT and DLPNO-CC methods and comparing these to the experimental spectrum using simulations. The results allow us to examine for the first time the distribution of spin densities and hyperfine coupling constants at the coupled cluster level, leading us to revisit the experimental assignment of the 33S hyperfine splitting. The wavefunction-based approach to obtain spin-dependent properties of open-shell systems demonstrated here for the case of azurin is transferable and applicable to a large array of bioinorganic systems

Spectroscopic and Theoretical Study on Siloxy-Based Molybdenum and Tungsten Alkylidyne Catalysts for Alkyne Metathesis

A combined spectroscopic and theoretical study on triphenyl- and dimethyl-phenyl siloxy molybdenum and tungsten alkylidyne catalysts for alkyne metathesis is reported. Using NMR, X-ray, UV-VIS, Resonance Raman spectroscopy and DFT calculations, the influence of different ligand systems and metal centers on the geometric and electronic structure and thermochemistry of different intermediates is investigated, that is the starting alkylidyne and the derived metallacyclobutadiene and metallatetrahedrane. This includes a mechanistic and kinetic study on the formation and isomerization of metallacyclobutadienes and metallatetrahedranes. Upon changing from monodentate to tripodal siloxy ligands, higher steric strain is imposed, which modulates the relative energies of the different intermediates. Additionally, intramolecular dispersion interactions between bound substrate and ligand can be operative. Tungsten as the central metal leads to stronger M-C σ-bonds, which overstabilize the reaction intermediates and preclude effective turnover. Furthermore, kinetic modeling strongly suggests that metallatetrahedranes are off-cycle intermediates based on the high barriers for direct formation but low barriers for isomerization from metallacyclobutadienes. We infer from our findings that effective catalysis can only be achieved when factors that (over)stabilize intermediates, such as strong M-C bonds or large dispersion interactions, are prevented by appropriate catalyst design

Productive Alkyne Metathesis with “Canopy Catalysts” Mandates Pseudorotation

Molybdenum alkylidyne complexes of the “canopy catalyst” series define new standards in the field of alkyne metathesis. The tripodal ligand framework lowers the symmetry of the metallacyclobutadiene complex formed by [2 + 2] cycloaddition with the substrate and imposes constraints onto the productive [2 + 2] cycloreversion; pseudorotation corrects this handicap and makes catalytic turnover possible. A combined spectroscopic, crystallographic, and computational study provides insights into this unorthodox mechanism and uncovers the role that metallatetrahedrane complexes play in certain cases

Reiniging van dunne meststromen door middel van elektrodialyse

Het Praktijkonderzoek Varkenshouderij onderzocht in samenwerking met Tauw Milieu bv in Deventer de mogelijkheden voor reiniging van dunne meststromen door middel van elektrodialyse. Reiniging tot de lozingsnormen voor het riool lijkt haalbaar. De kosten voor het proces op boerderijschaal zijn echter vooralsnog te hoog

Selecting a single orientation for millimeter sized graphene sheets

We have used Low Energy Electron Microscopy (LEEM) and Photo Emission Electron Microscopy (PEEM) to study and improve the quality of graphene films grown on Ir(111) using chemical vapor deposition (CVD). CVD at elevated temperature already yields graphene sheets that are uniform and of monatomic thickness. Besides domains that are aligned with respect to the substrate, other rotational variants grow. Cyclic growth exploiting the faster growth and etch rates of the rotational variants, yields films that are 99 % composed of aligned domains. Precovering the substrate with a high density of graphene nuclei prior to CVD yields pure films of aligned domains extending over millimeters. Such films can be used to prepare cluster-graphene hybrid materials for catalysis or nanomagnetism and can potentially be combined with lift-off techniques to yield high-quality, graphene based electronic devices

Effects of deposition dynamics on epitaxial growth

The dynamic effects, such as the steering and the screening effects during deposition, on an epitaxial growth (Cu/Cu(001)), is studied by kinetic Monte Carlo simulation that incorporates molecular dynamic simulation to rigorously take the interaction of the deposited atom with the substrate atoms into account. We find three characteristic features of the surface morphology developed by grazing angle deposition: (1) enhanced surface roughness, (2) asymmetric mound, and (3) asymmetric slopes of mound sides. Regarding their dependence on both deposition angle and substrate temperature, a reasonable agreement of the simulated results with the previous experimental ones is found. The characteristic growth features by grazing angle deposition are mainly caused by the inhomogeneous deposition flux due to the steering and screening effects, where the steering effects play the major role rather than the screening effects. Newly observed in the present simulation is that the side of mound in each direction is composed of various facets instead of all being in one selected mound angle even if the slope selection is attained, and that the slope selection does not necessarily mean the facet selection.Comment: 9 pages, 10 figure