Dynamic response of chlorine atoms on a RuO(2)(110) model catalyst surface

The dynamic behavior of surface accommodated chlorine atoms on RuO(2)(110) was studied by a variety of experimental methods including high resolution core level shift, thermal desorption-, and in situ infrared spectroscopy as well as in situ surface X-ray diffraction in combination with state-of-the-art density functional theory calculations. On the chlorinated RuO(2)(110) surface the undercoordinated oxygen atoms have been selectively replaced by chlorine. These strongly bound surface chlorine atoms shift from bridging to on-top sites when the sample is annealed in oxygen, while the reverse shift of Cl from on-top into bridge positions is observed during CO exposure; the vacant bridge position is then occupied by either chlorine or CO. For the CO oxidation reaction over chlorinated RuO(2)(110), the reactant induced site switching of chlorine causes a site-blocking of the catalytically active one-fold coordinatively unsaturated (1f-cus) Ru sites. This site blocking reduces the number of active sites and, even more important, on-top Cl blocks the free migration of the adsorbed reactants along the one-dimensional 1f-cus Ru rows, thus leading to a loss of catalytic activity.     

Covering properties of ideals

Elekes proved that any infinite-fold cover of a σ-finite measure space by a sequence of measurable sets has a subsequence with the same property such that the set of indices of this subsequence has density zero. Applying this theorem he gave a new proof for the random-indestructibility of the density zero ideal. He asked about other variants of this theorem concerning I-almost everywhere infinite-fold covers of Polish spaces where I is a σ-ideal on the space and the set of indices of the required subsequence should be in a fixed ideal ${{\mathcal{J}}}$ on ω. We introduce the notion of the ${{\mathcal{J}}}$ -covering property of a pair ${({\mathcal{A}}, I)}$ where ${{\mathcal{A}}}$ is a σ-algebra on a set X and ${{I \subseteq \mathcal{P}(X)}}$ is an ideal. We present some counterexamples, discuss the category case and the Fubini product of the null ideal ${\mathcal{N}}$ and the meager ideal ${\mathcal{M}}$ . We investigate connections between this property and forcing-indestructibility of ideals. We show that the family of all Borel ideals ${{\mathcal{J}}}$ on ω such that ${\mathcal{M}}$ has the ${{\mathcal{J}}}$ -covering property consists exactly of non weak Q-ideals. We also study the existence of smallest elements, with respect to Katětov–Blass order, in the family of those ideals ${\mathcal{J}}$ on ω such that ${\mathcal{N}}$ or ${\mathcal{M}}$ has the ${\mathcal{J}}$ -covering property. Furthermore, we prove a general result about the cases when the covering property “strongly” fails.     

Non-planar grain boundary structures in fcc metals and their role in nano-scale deformation mechanisms

This work presents the results of a comparative molecular dynamics study showing that relaxed random grain boundary structures can be significantly non-planar at the nano-scale in fcc metals characterized by low stacking fault values. We studied the relaxed structures of random [1?1?0] tilt boundaries in a polycrystal using interatomic potentials describing Cu and Pd. Grain boundaries presenting non-planar features were observed predominantly for the Cu potential but not for the Pd potential, and we relate these differences to the stacking fault values. We also show that these non-planar structures can have a strong influence on dislocation emission from the grain boundaries as well as on grain boundary strain accommodation processes, such as grain boundary sliding. We studied the loading response in polycrystals of 40 nm grain size to a level of 9% strain and found that the non-planar grain boundaries favour dislocation emission as a deformation mechanism and hinder grain boundary sliding. This has strong implications for the mechanical behaviour of nano-crystalline materials, which is determined by the competition between dislocation activity and grain boundary accommodation of the strain. Thus, the two interatomic potentials for Cu and Pd considered in this work resulted in the same overall stress–strain curve, but significantly different fractions of the strain accommodated by the intergranular versus intragranular deformation mechanisms. Strain localization patterns are also influenced by the non-planarity of the grain boundary structures.     

Rate constant for the reaction of CH3C(O)CH2 radical with HBr and its thermochemical implication

The fast flow method with laser induced fluorescence detection of CH₃C(O)CH₂ was employed to obtain the rate constant of k₁ (298 K) = (1.83 ± 0.12 (1σ)) × 10¹⁰ cm³ mol^?1 s^?1 for the reaction CH₃C(O)CH₂ + HBr ? CH₃C(O)CH₃ + Br (1, ?1). The observed reduced reactivity compared with n‐alkyl or alkoxyl radicals can be attributed to the partial resonance stabilization of the acetonyl radical. An application of k₁ in a third law estimation provides Δ_fH(CH₃C(O)CH₂) values of ?24 kJ mol^?1 and ?28 kJ mol^?1 depending on the rate constants available for reaction ( ‐1 ) from the literature. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 38: 32–37, 2006     

A compact microchip atomic clock based on all-optical interrogation of ultra-cold trapped Rb atoms

We propose a compact atomic clock that uses all-optical interrogation of ultra-cold Rb atoms that are magnetically trapped near the surface of an atom microchip. The interrogation scheme, which combines electromagnetically induced transparency with Ramsey’s method of separated oscillatory fields, can achieve an atomic shot-noise-level performance better than $10^{-13}/\sqrt{\tau}$ for 10⁶ atoms. A two-color Mach–Zehnder interferometer can detect a 100-pW probe beam at the optical shot-noise level using conventional photodetectors. This measurement scheme is nondestructive and therefore can be used to increase the operational duty cycle by reusing the trapped atoms for multiple clock cycles. Numerical calculations of the density matrix equations are used to identify realistic operating parameters at which AC Stark shifts are eliminated. By considering fluctuations in these parameters, we estimate that AC Stark shifts can be canceled to a level better than 2×10^?14. An overview of the apparatus is presented with estimates of cycle time and power consumption.     

“First‐Principles” kinetic monte carlo simulations revisited: CO oxidation over RuO2(110)

First principles‐based kinetic Monte Carlo (kMC) simulations are performed for the CO oxidation on RuO₂(110) under steady‐state reaction conditions. The simulations include a set of elementary reaction steps with activation energies taken from three different ab initio density functional theory studies. Critical comparison of the simulation results reveals that already small variations in the activation energies lead to distinctly different reaction scenarios on the surface, even to the point where the dominating elementary reaction step is substituted by another one. For a critical assessment of the chosen energy parameters, it is not sufficient to compare kMC simulations only to experimental turnover frequency (TOF) as a function of the reactant feed ratio. More appropriate benchmarks for kMC simulations are the actual distribution of reactants on the catalyst's surface during steady‐state reaction, as determined by in situ infrared spectroscopy and in situ scanning tunneling microscopy, and the temperature dependence of TOF in the from of Arrhenius plots. © 2012 Wiley Periodicals, Inc.     

Comparison of chemometric methods in the analysis of pharmaceuticals with hyperspectral Raman imaging

Chemical imaging method of vibrational spectroscopy, which provides both spectral and spatial information, creates a three‐dimensional (3D) dataset with a huge amount of data. When the components of the sample are unknown or their reference spectra are not available, the classical least squares (CLS) method cannot be applied to create visualized distribution maps. Raman image datasets can be evaluated even in such cases using multivariate (chemometric) methods for extracting the needed hidden information. The capability of chemometrics‐assisted Raman mapping is evaluated through the analysis of pharmaceutical tablets (considered as unknown) with the aim of estimating the pure component spectra based on the collected Raman image. Six chemometric methods, namely, principal component analysis (PCA), maximum autocorrelation factors (MAF), sample–sample 2D correlation spectroscopy (SS2D), self‐modeling mixture analysis (SMMA), multivariate curve resolution–alternating least squares (MCR‐ALS), and positive matrix factorization (PMF), were compared. SMMA was found to be the best choice to determine the number of components. MCR‐ALS and PMF provided the pure component spectra with the highest quality. MCR‐ALS was found to be superior to PMF in the estimation of Raman scores (which correspond to the concentrations) and yielded almost the same results as CLS (using the real reference spectra). Thus, the combination of Raman mapping and chemometrics could be successfully used to characterize unknown pharmaceuticals, identify their ingredients, and obtain information about their structures. This may be useful in the struggles against illegal and counterfeit products and also in the field of pharmaceutical industry when contaminants are to be identified. Copyright © 2011 John Wiley & Sons, Ltd.     

Explodator and oregonator: Parallel and serial oscillatory networks. A comparison

The antagonistic feedback concept of chemical oscillations is applied to derive and to compare the two different mechanisms. The delicate stoichiometry of the Oregonator causes difficulties in the modelling of real systems. The Explodator is relatively free of such problems.

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Picosecond laser plasma creation in the presence of high electrostatic field on the surface of metals

Plasma was created by picosecond Nd-laser pulses on metal surfaces. In contrast to usual experiments the plasma was created in the presence of strong outer electrostatic field. In addition to strong ion and electron emission, very intense X-ray radiation was also observed, the intensity and energy of which depended to a very great extent both on the value and the polarity of the outer electrostatic field.     

The ( g - 1)-support cover of the canonical locus

Journal d'Analyse Mathématique -