Die Analyse von Gemischen von Parazetaldehyd und Azetal

Ohne Zusammenfassung     

Using the local density approximation and the LYP,BLYP and B3LYP functionals within reference-state one-particle density-matrix theory

For closed-shell systems, the local density approximation (LDA) and the LYP, BLYP and B3LYP functionals are shown to be compatible with reference-state one-particle density-matrix theory, where this recently introduced formalism is based on Brueckner-orbital theory and an energy functional that includes exact exchange and a non-universal correlation-energy functional. The method is demonstrated to reduce to a density functional theory when the exchange-correlation energy-functional has a simplified form, i.e. its integrand contains only the coordinates of two electrons, say r ₁ and r ₂, and it has a Dirac delta function δ(r ₁ - r ₂ as a factor. Since Brueckner and Hartree–Fock orbitals are often very similar, any local exchange functional that works well with Hartree–Fock theory is a reasonable approximation with reference-state one-particle density-matrix theory. The LDA approximation is also a reasonable approximation. However, the Colle–Salvetti correlation-energy functional and the LYP variant are not ideal for the method, since these are universal functionals. Nevertheless, they appear to provide reasonable approximations. The B3LYP functional is derived using a linear combination of two functionals: one is the BLYP functional; the other uses exact exchange and a correlation-energy functional from the LDA.     

Cracking study of pentakis(dimethylamino)tantalum vapors by Knudsen cell mass spectrometry

Organometallic molecules are commonly used as gaseous precursors in Atomic Layer Deposition/Chemical Vapor Deposition (ALD/CVD) processes. However, the use of these molecules, which are generally thermally unstable at temperatures close to the deposition temperature, requires an understanding of their gas‐phase chemical behavior. The thermal cracking of the gaseous precursor, pentakis(dimethylamino) tantalum (PDMAT), generally adopted in the ALD/CVD TaN deposition processes, has been studied in the temperature range from 343 to 723K using a specific reactor coupled with a high‐temperature mass spectrometer. This reactor – built as tandem Knudsen cells – consists of two superimposed cells. The first stage reactor – an evaporation cell – provides an input saturated vapor flow operating from room temperature to 333K. The second stage cell, named the cracking cell, operated from 333 to 723K in the present study. Experiments showed the appearance of many gaseous species when the cracking temperature increased and, in particular, dimethylamine, corresponding to the saturated organic branches of PDMAT. Decomposition products of the HNC₂H₆ branch were observed at relatively high temperature, namely above 633K. This gas‐phase study – as for the preceding saturated one – shows the presence of oxygen‐containing molecules in PDMAT cracked vapor. Thus, it explains the systematic presence of oxygen contamination in the deposited TaN films observed in ALD/CVD industrial processes. Copyright © 2010 John Wiley & Sons, Ltd.     

A special reactor coupled with a high‐temperature mass spectrometer for the investigation of the vaporization and cracking of organometallic compounds

A special reactor coupled to a high‐temperature mass spectrometer was specifically designed for the study of vaporization and thermal cracking of organometallic precursors. This reactor has two kinds of settings. One is a single Knudsen effusion cell which enables the analysis of the composition of saturated vapors and the determination of the partial pressure of each gaseous molecule in equilibrium with its condensed phase. This cell is an evaporation/sublimation cell (operating from 243 to 473 K), which can be tightly closed – like a vacuum chamber – in order to protect organometallic compounds against moisture and atmospheric components. This cell can be independently weighed usefully to evaluate the equilibrium vapor pressures of the sample using the mass‐loss method. During experiments, the effusion aperture is externally opened for direct mass spectrometric measurements. The other setting dedicated to the study of thermal decomposition of gaseous molecules consists of a set of tandem cells: the previously described Knudsen cell and a cracking cell (operating from 293 to 973 K). Copyright © 2009 John Wiley & Sons, Ltd.     

Efficient Algorithms for Bayesian Nearest Neighbor Gaussian Processes

We consider alternate formulations of recently proposed hierarchical nearest neighbor Gaussian process (NNGP) models for improved convergence, faster computing time, and more robust and reproducible Bayesian inference. Algorithms are defined that improve CPU memory management and exploit existing high-performance numerical linear algebra libraries. Computational and inferential benefits are assessed for alternate NNGP specifications using simulated datasets and remotely sensed light detection and ranging data collected over the U.S. Forest Service Tanana Inventory Unit (TIU) in a remote portion of Interior Alaska. The resulting data product is the first statistically robust map of forest canopy for the TIU. Supplemental materials for this article are available online.     

Optically probing spin and charge interactions in a tunable artificial molecule

We optically probe and electrically control a single artificial molecule containing a well defined number of electrons. Charge and spin dependent interdot quantum couplings are probed optically by adding a single electron-hole pair and detecting the emission from negatively charged exciton states. Coulomb- and Pauli-blockade effects are directly observed, and tunnel coupling and electrostatic charging energies are independently measured. The interdot quantum coupling is shown to be mediated by electron tunneling. Our results are in excellent accord with calculations that provide a complete picture of negative excitons and few-electron states in quantum dot molecules.     

First observation of the Greisen-Zatsepin-Kuzmin suppression

The High Resolution Fly's Eye (HiRes) experiment has observed the Greisen-Zatsepin-Kuzmin suppression (called the GZK cutoff) with a statistical significance of five standard deviations. HiRes' measurement of the flux of ultrahigh energy cosmic rays shows a sharp suppression at an energy of 6 x 10(19) eV, consistent with the expected cutoff energy. We observe the ankle of the cosmic-ray energy spectrum as well, at an energy of 4 x 10(18) eV. We describe the experiment, data collection, and analysis and estimate the systematic uncertainties. The results are presented and the calculation of the statistical significance of our observation is described.     

Aromatic substitution of 4-phenylisothiazole

Aromatic substitutions on 4-phenylisothiazole by nitric acid, halogens, chlorosulfonic acid and acetic anhydride take place under relatively mild conditions to give predominantly para and ortho substitution on the benzene ring. By contrast, the 3-isothiazolyl group has been shown to be meta directing. Several derivatives of 4-phenylisothiazole are described.     

Inverted electron-hole alignment in InAs-GaAs self-assembled quantum dots

New information on the electron-hole wave functions in InAs-GaAs self-assembled quantum dots is deduced from Stark effect spectroscopy. Most unexpectedly it is shown that the hole is localized towards the top of the dot, above the electron, an alignment that is inverted relative to the predictions of all recent calculations. We are able to obtain new information on the structure and composition of buried quantum dots from modeling of the data. We also demonstrate that the excited state transitions arise from lateral quantization and that tuning through the inhomogeneous distribution of dot energies can be achieved by variation of electric field.     

Novel use of glow discharge optical emission spectroscopy (GDOES) to study corrosion of AA2024‐T3 in the presence and absence of inhibitors

Elemental depth profiling by glow discharge optical emission spectroscopy has been used to characterise the corrosion products on AA2024‐T3. In previous work, the aluminium, oxygen and copper depth profiles were shown to provide information regarding surface roughening, the thickness of corroded layers and extent of copper de‐alloying/relocation. In the present work, the study is extended to the detection of corrosion inhibitors deposited on the exposed alloy surface in a model defect. The work includes a comparison of hybrid coatings doped with inhibitors encapsulated in nanocontainers and with the direct addition of inhibitor species to the coating matrix. The work also investigates the effects of inhibitor addition to sol–gel coatings or primer systems or both, highlighting the possible synergistic effects of mixed inhibitor systems. Copyright © 2015 John Wiley & Sons, Ltd.