Comparison of the Hartree-Fock,Møller-Plesset,and Hartree-Fock-Slater method with respect to electrostatic properties of small molecules

Summary The results of various quantum chemical calculations, the Hartree-Fock (HF) method, the Møller-Plesset perturbation theory (MP2), and the Hartree-Fock-Slater (HFS) method are compared. Atomic charges, dipole moments, topological properties of the electron density distribution and polarizabilities, and first hyperpolarizabilities are calculated. Atomic charges obtained with the HFS method are found to be very close to those calculated with the MP2 method, from which we conclude that the HFS method describes to some extent electron correlation effects. Performing an MP2 calculation after an HF calculation improves the molecular dipole moments considerably, yielding values close to the experimental ones. HFS calculations are computationally less demanding than MP2 and yield comparable results for the electron density distributions, dipole moments and polarizabilities.     

Long‐Range Domain Structure and Symmetry Engineering by Interfacial Oxygen Octahedral Coupling at Heterostructure Interface

In epitaxial thin film systems, the crystal structure and its symmetry deviate from the bulk counterpart due to various mechanisms such as epitaxial strain and interfacial structural coupling, which is accompanyed by a change in their properties. In perovskite materials, the crystal symmetry can be described by rotations of sixfold coordinated transition metal oxygen octahedra, which are found to be altered at interfaces. Here, it is unraveled how the local oxygen octahedral coupling at perovskite heterostructural interfaces strongly influences the domain structure and symmetry of the epitaxial films resulting in design rules to induce various structures in thin films using carefully selected combinations of substrate/buffer/film. Very interestingly it is discovered that these combinations lead to structure changes throughout the full thickness of the film. The results provide a deep insight into understanding the origin of induced structures in a perovskite heterostructure and an intelligent route to achieve unique functional properties.     

Pulsed laser deposition: metal versus oxide ablation

We present experimental results of pulsed laser interaction with metal (Ni, Fe, Nb) and oxide (TiO₂, SrTiO₃, BaTiO₃) targets. The influence of the laser fluence and the number of laser pulses on the resulting target morphology are discussed. Although different responses for metal and oxide targets to repetitive laser irradiation could be expected due to the different band structures of metals and oxides, the optical response is quite similar for 248-nm laser irradiation. Therefore, the difference in response is largely caused by differences in thermal properties. Metal targets show periodic structures of the order of micrometers after consecutive pulses of laser radiation, while the SrTiO₃ and BaTiO₃ targets show a flat surface after ablation for relatively low fluences (1.0 Jcm^-2). The observed TiO₂ target ablation characteristics fall in between those of the ablated metals and perovskites, because ablation results in the presence of Ti-rich material, which shields the underlying stoichiometric target material from ablation. The final target morphology is dependent on fluence, number of pulses, and the movement of the target itself (rotating, scanning, or stationary). It can take between 15 and 75 pulses to reach a steady-state target morphology on a stationary target. PACS 79.20.Ds; 52.38.Mf; 81.15.Fg     

A conservative unstructured scheme for rapidly varied flows

This article introduces a new semi‐implicit, staggered finite volume scheme on unstructured meshes for the modelling of rapidly varied shallow water flows. Rapidly varied flows occur in the inundation of dry land during flooding situations. They typically involve bores and hydraulic jumps after obstacles such as road banks. Near such sudden flow transitions, the grid resolution is often low compared with the gradients of the bathymetry. Locally the hydrostatic pressure assumption may become invalid. In these situations, it is crucial to apply the correct conservation properties to obtain accurate results. An important feature of this scheme is therefore its ability to conserve momentum locally or, by choice, preserve constant energy head along a streamline. This is achieved using a special interpolation method and control volumes for momentum. The efficiency of inundation calculations with locally very high velocities, and in the case of unstructured meshes locally very small grid distances, is severely hampered by the Courant condition. This article provides a solution in the form of a locally implicit time integration for the advective terms that allows for an explicit calculation in most of the domain, while maintaining unconditional stability by implicit calculations only where necessary. The complex geometry of flooded urban areas asks for the flexibility of unstructured meshes. The efficient calculation of the pressure gradient in this, and other semi‐implicit staggered schemes, requires, however, an orthogonality condition to be put on the grid. In this article a simple method is introduced to generate unstructured hybrid meshes that fulfil this requirement. Copyright © 2008 John Wiley & Sons, Ltd.     

Patterning of Epitaxial Perovskites from Micro and Nano Molded Stencil Masks

A process is developed that combines soft lithographic molding with pulsed laser deposition (PLD) to make heteroepitaxial patterns of functional perovskite oxide materials. Micro‐ and nanostructures of sacrificial ZnO are made by micro molding in capillaries (MiMiC) and nano transfer molding, respectively, and used to screen the single crystalline substrates during subsequent PLD. ZnO is used because of its compatibility with the high temperatures reached during PLD and because of the ease of its removal after use by benefiting from its amphoteric nature. Sub‐micrometer sized lines of La_0.67Sr_0.33MnO₃ are made by the transfer molding approach, preserving the anisotropic features expected for a fully oriented thin film and taking account for the magnetostatic contribution from the line shapes. Different patterns of SrRuO₃ are made with lateral dimensions of a few micrometers having individual features for which electrical isolation is illustrated. The bottom‐up soft lithographic methods can be compliantly utilized for making epitaxial structures of various shapes and sizes in the μm down to the nm range, and offer unique opportunities for fundamental studies as well as for realizing technological applications.     

Pulsed laser deposition of PZT/Pt composite thin films with high dielectric constants

PbZr_0.53Ti_0.47O₃ (PZT) thin films containing nanoparticles of Pt (3–10 nm) were produced using pulsed laser deposition (PLD). The Pt content can be tuned by varying the energy density of the laser beam. Phase and microstructure analysis of the thin films was performed using XRD, SEM, TEM and AFM. The electrical properties were investigated by C–V and I–V measurements. The effective dielectric constant of the composite films increased substantially through the Pt dispersion. These films are promising candidates, for instance, for high-density dynamic random access memory (DRAM) devices. PACS 77.22.Ch; 77.84.Lf; 81.15.Fg     

Biomimetic synthesis of neodihydrothebaine and bractazonine from thebaine

Photochemical irradiation of the morphinan alkaloid thebaine 1 followed by reduction, affords the dibenz[d,f]azonine alkaloids neodihydrothebaine 2 and bractazonine 3, in a sequence paralleling the proposed biosynthesis of these alkaloids in Papaver bracteatum.     

Some rapid identification methods in gas chromatography

Summary Three methods are described for the rapid identification of the effluents of a gas Chromatographic column with relatively simple means: 1.Oxidation of the effluent and separation of the oxidation products to find C/H and C/N ratios. 2. Continuous hydrogenation of the effluent to obtain semiquantitative information of the amounts of sulphur, halogen and oxygen present. 3. Identification of halogen-containing compounds by means of a Beilstein detector.

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Zusammenfassung Folgende drei Verfahren zur schnellen und relativ einfach ausführbaren Identifizierung der Bluate gaschromatographischer Säulen werden beschrieben: 1.Oxydation des Eluats und Trennung der Oxydationsprodukte zur Bestimmung der Verhältnisse C/H und C/N. 2. Kontinuierliche Hydrierung des Bluats zur semiquantitativen Bestimmung von Schwefel, Halogen und Sauerstoff. 3. Identifizierung halogenhaltiger Verbindungen mit Hilfe eines Beilstein-Detektors.

     

Band-broadening in packed chromatographic columns

In the past few years some problems have arisen as to the interpretation of experimental plate height data of packed chromatographic columns by means of the theory of VAN DEEMTER et al. These difficulties concern the “eddy diffusion” and “mass transfer” terms in particular. Light may be thrown on this matter by the recognition of unevenness of flow throughout the column cross-section as a major source of band-broadening. By considering the contribution to plate height resulting from the interaction between such flow profiles and various mechanisms of lateral transport of material it proved possible to solve the above-mentioned difficulties.     

Resonant soft x-ray scattering from stepped surfaces of SrTiO3

We studied the resonant diffraction signal from stepped surfaces of SrTiO(3) at the Ti 2p → 3d (L(2,3)) resonance in comparison with x-ray absorption (XAS) and specular reflectivity data. The steps on the surface form an artificial superstructure suitable as a model system for resonant soft x-ray diffraction. A small step density on the surface is sufficient to produce a well defined diffraction peak. We determined the optical parameters of the sample across the resonance and found that the differences between the energy dependence of the x-ray absorption signal, the specular reflectivity and the step-related peak reflect the different quantities probed in these signals. When recorded at low incidence or detection angles, XAS and specular reflectivity spectra are strongly distorted by the changes of the angle of total reflection with energy. The resonant diffraction spectrum is less affected and can be used as a spectroscopic probe even in less favorable geometries.