A non-singular spherically symmetric separable copy of the vacuum in SU(2) Landau gauge

We give a new non-singular spherically symmetric and separable copy of the vacuum in Landau gauge for SU(2) Yang-Mills theories. The solution can be considered as a generalization of Gribov's solution in Coulomb gauge and thus it demonstrates the similarity between vacua in Coulomb and Landau gauges.     

Synthesis and characterization of a silyl substituted bis(indenyl) zirconium dichloride and comparison of its olefin polymerization behavior to a siloxy substituted analogue

The synthesis and characterization of rac‐[ethylenebis(1‐(tert‐butyldimethylsilyl)‐3‐indenyl)]zirconium dichloride ( 3 ) is reported. The silyl substituted 3 /MAO was compared to its siloxy substituted analogue ( 4 ) in ethylene homo‐ and in ethylene‐1‐hexene copolymerizations to elucidate the effect of the heteroatom on polymerization performance. The influence of monomer and cocatalyst concentration and the polymerization temperature was investigated. The oxygen between the indenyl ligand and the bulky tert‐butyldimethylsilyl group in the siloxy substituted 4 /MAO was found to have a positive influence on polymerization activity and copolymerization performance. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 127–133, 2001     

Über die Bildung von Thiazolderivaten aus Harnsäure

Ohne Zusammenfassung     

Über die Einwirkung des Bromwasserstoffs und der Schwefelsäure auf primäre Alkohole

Ohne Zusammenfassung     

Combined time- and space-resolved Raman spectrometer for the non-invasive depth profiling of chemical hazards

A time-resolved inverse spatially offset Raman spectrometer was constructed for depth profiling of Raman-active substances under both the lab and the field environments. The system operating principles and performance are discussed along with its advantages relative to traditional continuous wave spatially offset Raman spectrometer. The developed spectrometer uses a combination of space- and time-resolved detection in order to obtain high-quality Raman spectra from substances hidden behind coloured opaque surface layers, such as plastic and garments, with a single measurement. The time-gated spatially offset Raman spectrometer was successfully used to detect concealed explosives and drug precursors under incandescent and fluorescent background light as well as under daylight. The average screening time was 50 s per measurement. The excitation energy requirements were relatively low (20 mW) which makes the probe safe for screening hazardous substances. The unit has been designed with nanosecond laser excitation and gated detection, making it of lower cost and complexity than previous picosecond-based systems, to provide a functional platform for in-line or in-field sensing of chemical substances.     

Photoinduced intra- and intermolecular electron transfer in solutions and in solid organized molecular assemblies

The present paper highlights results of a systematic study of photoinduced electron transfer, where the fundamental aspects of the photochemistry occurring in solutions and in artificially or self-assembled molecular systems are combined and compared. In photochemical electron transfer (ET) reactions in solutions the electron donor, D, and acceptor, A, have to be or to diffuse to a short distance, which requires a high concentration of quencher molecules and/or long lifetimes of the excited donor or acceptor, which cannot always be arranged. The problem can partly be avoided by linking the donor and acceptor moieties covalently by a single bond, molecular chain or chains, or rigid bridge, forming D-A dyads. The covalent combination of porphyrin or phthalocyanine donors with an efficient electron acceptor, e.g. fullerene, has a two-fold effect on the electron transfer properties. Firstly, the electronic systems of the D-A pair result in a formation of an exciplex intermediate upon excitation both in solutions and in solid phases. The formation of the exciplex accelerates the ET rate, which was found to be as fast as >10(12) s(-1). Secondly, the total reorganization energy can be as small as 0.3 eV, even in polar solvents, which allows nanosecond lifetimes for the charge separated (CS) state. Molecular assemblies can form solid heterogeneous, but organized systems, e.g. molecular layers. This results in more complex charge separation and recombination dynamics. A distinct feature of the ET in organized assemblies is intermolecular interactions, which open a possibility for a charge migration both in the acceptor and in the donor layers, after the primary intramolecular exciplex formation and charge separation in the D-A dyad. The intramolecular ET is fast (35 ps) and efficient, but the formed interlayer CS states have lifetimes in microsecond or even second time domain. This is an important result considering possible applications.     

Azafullerene C59N–Phthalocyanine Dyad: Synthesis,Characterisation and Photoinduced Electron Transfer

The synthesis of a new azafullerene C₅₉N–phthalocyanine (Pc) dyad is described. The key step for the synthesis of the C₅₉N–Pc dyad was the formation of the C₅₉N‐based carboxylic acid, which was smoothly condensed with hydroxy‐modified Pc. The structure of the C₅₉N–Pc dyad was verified by ¹H and ¹³C NMR spectroscopy, IR spectroscopy, UV/Vis spectroscopy and MS measurements. The photophysical and electrochemical properties of the C₅₉N–Pc dyad were investigated in both polar and non‐polar solvents by steady state and time‐resolved photoluminescence and absorption spectroscopy, as well as by cyclic voltammetry. Different relaxation pathways for the photoexcited C₅₉N–Pc dyad, as a result of changing the solvent polarity, were found, thus giving rise to energy‐transfer phenomena in non‐polar toluene and charge‐transfer processes in polar benzonitrile. Finally, the detailed quenching mechanisms were evaluated and compared with that of a C₆₀–Pc dyad, which revealed that the different excited‐state energies and reduction potentials of the two fullerene spheres (i.e. C₅₉N vs. C₆₀) strongly diverged in the deactivation pathways of the excited states of the corresponding phthalocyanine dyads.     

Effect of modifier structure in the enantioselective hydrogenation of 1-phenyl-1,2-propanedione

Three different modifiers, (-)-cinchonidine, 10,11-dihydrocinchonidine and (+)-cinchonine were investigated in the enantioselective hydrogenation of an unsymmetrical dione, 1-phenyl-1,2-propanedione, over a commercial Pt/Al₂O₃ catalyst. The catalytic activity, as well as the regio- and enantioselectivity in the hydroxyketones and diols formed were compared.     

The affine equivariant sign covariance matrix: asymptotic behavior and efficiencies

We consider the affine equivariant sign covariance matrix (SCM) introduced by Visuri et al. (J. Statist. Plann. Inference 91 (2000) 557). The population SCM is shown to be proportional to the inverse of the regular covariance matrix. The eigenvectors and standardized eigenvalues of the covariance matrix can thus be derived from the SCM. We also construct an estimate of the covariance and correlation matrix based on the SCM. The influence functions and limiting distributions of the SCM and its eigenvectors and eigenvalues are found. Limiting efficiencies are given in multivariate normal and t-distribution cases. The estimates are highly efficient in the multivariate normal case and perform better than estimates based on the sample covariance matrix for heavy-tailed distributions. Simulations confirmed these findings for finite-sample efficiencies.     

Interweaving Markov Chain Monte Carlo Strategies for Efficient Estimation of Dynamic Linear Models

In dynamic linear models (DLMs) with unknown fixed parameters, a standard Markov chain Monte Carlo (MCMC) sampling strategy is to alternate sampling of latent states conditional on fixed parameters and sampling of fixed parameters conditional on latent states. In some regions of the parameter space, this standard data augmentation (DA) algorithm can be inefficient. To improve efficiency, we apply the interweaving strategies of Yu and Meng to DLMs. For this, we introduce three novel alternative DAs for DLMs: the scaled errors, wrongly scaled errors, and wrongly scaled disturbances. With the latent states and the less well known scaled disturbances, this yields five unique DAs to employ in MCMC algorithms. Each DA implies a unique MCMC sampling strategy and they can be combined into interweaving and alternating strategies that improve MCMC efficiency. We assess these strategies using the local level model and demonstrate that several strategies improve efficiency relative to the standard approach and the most efficient strategy interweaves the scaled errors and scaled disturbances. Supplementary materials are available online for this article.