Neutron scattering study on CeAgAs2

CeAgAs₂, an HfCuSi₂ like layered pnictide, orders antiferromagnetically at T_N=6.2(1) K. The ordering process was monitored in neutron diffraction experiments in the temperature range 10 K≥T≥3.5 K. At T=4 K the lattice parameters are a=5.7438(1) Å, b=5.7696(1) Å and c=21.0067(2) Å. The diffraction pattern of the antiferromagnetic phase with a propagation vector k=[0,0,0] point towards ferromagnetically ordered moments in Ce layers stacked along [001], the individual layers are coupled antiferromagnetically with a +− −+type sequence. The alignment of moments within the Ce layers cannot be determined reliably from the experimental data so that two different structure models are discussed. The proposed metamagnetic transition was confirmed by diffraction experiments applying an external magnetic field at T<T_N. In the interval 4 K≤T≤6 K, a relatively small field of μ₀H≈0.3 T suffices to fully suppress the antiferromagnetic ordering. The effect is completely reversible yet subject to hysteresis: After switching off the external field at any T<T_N the magnetic reflections gain their original intensity within several 10 min indicating the restoring of the antiferromagnetic phase.     

Island shapes and aggregation steered by the geometry of the substrate lattice

We find that island shapes and aggregation in diindenoperylene deposited on Au(100), Au(110), and Au(111) single crystals are steered by the anisotropy due to the lattice geometry of the substrate. This phenomenon may be exploited as a tool for molecular patterning of surfaces.     

New Cu-based catalysts supported on TiO2 films for Ullmann S(N)Ar-type C-O coupling reactions

New routes for the preparation of highly active TiO(2)-supported Cu and CuZn catalysts have been developed for C-O coupling reactions. Slurries of a titania precursor were dip-coated onto glass beads to obtain either structured mesoporous or non-porous titania thin films. The Cu and CuZn nanoparticles, synthesized using a reduction by solvent method, were deposited onto calcined films to obtain a Cu loading of 2 wt%. The catalysts were characterized by inductively coupled plasma (ICP) spectroscopy, temperature-programmed oxidation/reduction (TPO/TPR) techniques, (63)Cu nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (S/TEM-EDX) and X-ray photo-electron spectroscopy (XPS). The activity and stability of the catalysts obtained have been studied in the C-O Ullmann coupling of 4-chloropyridine and potassium phenolate. The titania-supported nanoparticles retained catalyst activity for up to 12 h. However, catalyst deactivation was observed for longer operation times due to oxidation of the Cu nanoparticles. The oxidation rate could be significantly reduced over the CuZn/TiO(2) catalytic films due to the presence of Zn. The 4-phenoxypyridine yield was 64% on the Cu/nonporous TiO(2) at 120 °C. The highest product yield of 84% was obtained on the Cu/mesoporous TiO(2) at 140 °C, corresponding to an initial reaction rate of 104 mmol g(cat) (-1) s(-1). The activation energy on the Cu/mesoporous TiO(2) catalyst was found to be (144±5) kJ mol(-1), which is close to the value obtained for the reaction over unsupported CuZn nanoparticles (123±3 kJ mol(-1)) and almost twice the value observed over the catalysts deposited onto the non-porous TiO(2) support (75±2 kJ mol(-1)).     

SIP: critical value functions have finite modulus of non-convexity

We consider semi-infinite programming problems ${{\rm SIP}(z)}$ depending on a finite dimensional parameter ${z \in \mathbb{R}^p}$ . Provided that ${\bar{x}}$ is a strongly stable stationary point of ${{\rm SIP}(\bar{z})}$ , there exists a locally unique and continuous stationary point mapping ${z \mapsto x(z)}$ . This defines the local critical value function ${\varphi(z) := f(x(z); z)}$ , where ${x \mapsto f(x; z)}$ denotes the objective function of ${{\rm SIP}(z)}$ for a given parameter vector ${z\in \mathbb{R}^p}$ . We show that ${\varphi}$ is the sum of a convex function and a smooth function. In particular, this excludes the appearance of negative kinks in the graph of ${\varphi}$ .     

Application of spectral filtering to discontinuous Galerkin methods on triangulations

We adapt the spectral viscosity (SV) formulation implemented as a modal filter to a discontinuous Galerkin (DG) method solving hyperbolic conservation laws on triangular grids. The connection between SV and spectral filtering, which is undertaken for the first time in the context of DG methods on unstructured grids, allows to specify conditions on the filter strength regarding time step choice and mesh refinement. A crucial advantage of this novel damping strategy is its low computational cost. We furthermore obtain new error bounds for filtered Dubiner expansions of smooth functions. While high order accuracy with respect to the polynomial degree N is proven for the filtering procedure in this case, an adaptive application is proposed to retain the high spatial approximation order. Although spectral filtering stabilizes the scheme, it leaves weaker oscillations. Therefore, as a postprocessing step, we apply the image processing technique of digital total variation (DTV) filtering in the new context of DG solutions and prove conservativity in the limit for this filtering procedure. Numerical experiments for scalar conservation laws confirm the designed order of accuracy of the DG scheme with adaptive modal filtering for polynomial degrees up to 8 and the viability of spectral and DTV filtering in case of shocks. © 2011 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 2011     

A theoretical investigation of the interaction between substituted carbonyl derivatives and water: Open or cyclic complexes?

The structures and binding energies of complexes between substituted carbonyl bases and water are the B3LYP/6‐311++G(d,p) computational level. The calculations also include the proton affinity (PA) of the O of the C?O group, the deprotonation enthalpies (DPE) of the CH bonds along a natural bond orbital analysis. The calculations reveal that stable open C?O···H_wO_w as well as cyclic CH···O_wH_w···O?C complexes are formed. The binding energies for the open complexes are linearly related to the PAs, whereas the binding energies for the cyclic complexes depend on both the PA and DPE. Different indicators of hydrogen bonds strength such as electron charge density, intramolecular and intermolecular hyperconjugation energy, occupation of orbitals, and charge transfer show significant differences between open and cyclic complexes. The contraction of the CH bond of the formyl group and the corresponding blue shift of the ν(CH) vibration are explained by the classical trans lone pair effect. In contrast, the elongation or contraction of the CH₃ group involved in the interaction with water results from the variation of the orbital interaction energies from the σ(CH) bonding orbital to the σ* and π* antibonding orbitals of the C?O group. The resulting blue or red shifts of the ν(CH₃) vibrations are calculated in the partially deuterated isotopomers. © 2012 Wiley Periodicals, Inc.     

A complete set of self‐consistent charge density‐functional tight‐binding parametrization of zinc chalcogenides (ZnX; X=O,S, Se,and Te)

We have developed a complete set of self‐consistent charge density‐functional tight‐binding parameters for Zn? X (X = Zn, O, S, Se, Te, Cd, H, C, and N). The transferability of the derived parameters has been tested against Pseudo Potential‐Perdew, Burke and Ernzerhof (PP‐PBE) calculations and experimental values (whenever available) for corresponding bulk systems (e.g., hexagonal close packing, zinc‐blende, and wurtzite(wz)), various kinds of nanostructures (such as nanowires, surfaces, and nanoclusters), and also some small molecular systems. Our results show that the derived parameters reproduce the structural and energetic properties of the above‐mentioned systems very well. With the derived parameter set, one can study zinc‐chalcogenide nanostructures of relatively large size which was otherwise prohibited by other methods. The Zn‐Cd parametrization developed in this article will help in studying large semiconductor hetero‐nanostructures of Zn and Cd chalcogenides such as ZnX/CdX core/shell nanoparticles, nanotubes, nanowires, and nanoalloys. © 2012 Wiley Periodicals, Inc.     

Rational cohomology of the free loop space of a simply connected 4-manifold

The purpose of this paper is to calculate the rational cohomology ${H^{\ast}(X^{{S}^{1}} ; \mathbb{Q})}$ of the free loop space for a simply connected closed 4-manifold X. We use minimal models, so the starting point is the cohomology algebra ${H^{\ast}(X; \mathbb{Q})}$ which depends only on the second Betti number b ₂ and the signature of X itself. Calculations of ${H^{\ast}(X^{{S}^{1}} ; \mathbb{Q})}$ for b ₂ ≤ 2 are known. We study the case b ₂ > 2. We obtain an explicit formula for Poincaré series of the space ${X^{{S}^{1}}}$ , with the second Betti number b ₂ as a parameter.     

<Emphasis Type="Italic">Q</Emphasis>-Manifolds and Mackenzie Theory

Double Lie algebroids were discovered by Kirill Mackenzie from the study of double Lie groupoids and were defined in terms of rather complicated conditions making use of duality theory for Lie algebroids and double vector bundles. In this paper we establish a simple alternative characterization of double Lie algebroids in a supermanifold language. Namely, we show that a double Lie algebroid in Mackenzie’s sense is equivalent to a double vector bundle endowed with a pair of commuting homological vector fields of appropriate weights. Our approach helps to simplify and elucidate Mackenzie’s original definition; we show how it fits into a bigger picture of equivalent structures on ‘neighbor’ double vector bundles. It also opens ways for extending the theory to multiple Lie algebroids, which we introduce here.