Kinetics and mechanism of the thermal decomposition reaction of acetone cyclic diperoxide in the gas phase

The kinetics of the thermal decomposition reaction of gaseous 3,3,6,6-tetramethyl-1,2,4,5-tetroxane (ACDP) in the presence of n-octane was studied in the 403.2–523.2 K temperature range. This reaction yields acetone as the organic product. Under optimum conditions, first-order kinetics were observed, included when the S/V ratio of the Pyrex reaction vessel was increased by a nearly six-fold factor. In the range 443.2–488.2 K the temperature dependence of the rate constants for the unimolecular reaction in conditioned vessels is given by In k₁/(s^?1) = (31.8 ± 2.5) ? [(39.0 ± 2.5)/RT]. The value of the energy of activation in kcal/mol correspond to one O? O bond homolysis of the ACDP molecule in a stepwise biradical initiated decomposition mechanism. At the lower reaction temperatures as well in preliminary experiments participation of a surface catalyzed ACDP decomposition process could be detected. © 1994 John Wiley & Sons, Inc.     

Interacting Spin 0 Fields with Torsion via Duffin-Kemmer-Petiau Theory

Here we study the behaviour of the spin 0 sector of the DKP field in spaces with torsion. First we show that in a Riemann-Cartan manifold the DKP field presents an interaction with torsion when minimal coupling is performed, contrary to the behaviour of the KG field, a result that breaks the usual equivalence between the DKP and the KG fields.Next we analyse the case of the Teleparallel Equivalent of General Relativity (Weitzenböck manifold), showing that in this case there is a perfect agreement between KG and DKP fields. The origins of both results are also discussed.On leave from     

Numerical treatment of an asset price model with non-stochastic uncertainty

In contrast to stochastic differential equation models used for the calculation of the term structure of interest rates, we develop an approach based on linear dynamical systems under non-stochastic uncertainty with perturbations. The uncertainty is described in terms of known feasible sets of varying parameters. Observations are used in order to estimate these parameters by minimizing the maximum of the absolute value of measurement errors, which leads to a linear or nonlinear semi-infinite programming problem. A regularized logarithmic barrier method for solving (ill-posed) convex semi-infinite programming problems is suggested. In this method a multi-step proximal regularization is coupled with an adaptive discretization strategy in the framework of an interior point approach. A special deleting rule permits one to use only a part of the constraints of the discretized problems. Convergence of the method and its stability with respect to data perturbations in the cone of convexC ¹-functions are studied. On the basis of the solutions of the semi-infinite programming problems a technical trading system for future contracts of the German DAX is suggested and developed. Supported by the Stiftung Rheinland/Pfalz für Innovation, No. 8312-386261/307.     

On the possibility of a radical decrease in the strength of many-body interactions in the organic metal α-(BETS)<Subscript>2</Subscript> KHg(SCN)<Subscript>4</Subscript>

Behavior of the de Haas-van Alphen (dHvA) oscillations depending on the angle between the magnetic field direction and the perpendicular to conducting layers in the quasi-two-dimensional organic metal α-(BETS)₂ KHg(SCN)₄ was studied in detail. The angular dependence of the dHvA oscillation amplitude exhibits a series of minima (at ±43.2°, ±64.6°, and ±72.0°) related to the “zero spin” effect, through which it is possible to estimate the splitting factor. An analysis of this value suggests that many-body interactions in the compound studied are either absent or at least radically weakened.     

LIDAR mapping of ozone-episode dynamics in Paris and intercomparison with spot analyzers Supplementary material available at http://link.springer.de/journals/apb

Continuous mapping of an ozone episode in Paris in June 1999 has been performed using a differential absorption lidar system. The 2D ozone concentration vertical maps recorded over 33 h at the Champ de Mars are compiled in a video clip that gives access to local photochemical dynamics with unprecedented precision. The lidar data are compared over the whole period with point monitors located at 0-, 50-, and 300-m altitudes on the Eiffel Tower. Very good agreement is found when spatial resolution, acquisition time, and required concentration accuracy are optimized. Sensitivity to these parameters for successful intercomparison in urban areas is discussed. Received: 11 February 2002 / Published online: 14 March 2002     

Current and shot noise in two capacitively coupled single electron transistors with an atomic sized spacer

The currents and their fluctuations in two capacitively coupled single electron transistors are determined in the limit of sequential tunnelling. Our considerations are restricted to the case when the islands (dots) of the transistors are atomic-sized, which means each of them has only one single electronic level available for the tunnelling processes. The Coulomb interactions of accumulated charges on the both single electron transistors lead to the effect of the negative differential resistance. An enhancement of the current shot-noise was also found. Spectral decomposition analysis indicated the two main contributions to the shot-noise: low- and high-frequency fluctuations. It was found that the low frequency fluctuations (polarization noise) are responsible for a strong enhancement of the current noise. Received 9 October 2001 / Received in final form 8 March 2002 Published online 9 July 2002     

Analysing the information flow between financial time series

Following the recently introduced concept of transfer entropy, we attempt to measure the information flow between two financial time series, the Dow Jones and DAX stock index. Being based on Shannon entropies, this model-free approach in principle allows us to detect statistical dependencies of all types, i.e. linear and nonlinear temporal correlations. However, when available data is limited and the expected effect is rather small, a straightforward implementation suffers badly from misestimation due to finite sample effects, making it basically impossible to assess the significance of the obtained values. We therefore introduce a modified estimator, called effective transfer entropy, which leads to improved results in such conditions. In the application, we then manage to confirm an information transfer on a time scale of one minute between the two financial time series. The different economic impact of the two indices is also recovered from the data. Numerical results are then interpreted on one hand as capability of one index to explain future observations of the other, and on the other hand within terms of coupling strengths in the framework of a bivariate autoregressive stochastic model. Evidence is given for a nonlinear character of the coupling between Dow Jones and DAX.     

Evolution of stress and strain relaxation of Ge and SiGe alloy films on Si(0 0 1)

The growth of Ge and SiGe alloy films on Si substrates has attracted considerable interest in the last years because of their importance for optoelectronic devices as well as Si-based high speed transistors. Here we give a short overview on our recent real time stress measurements of Ge and SiGe alloy films on Si(0 0 1) performed with a sensitive cantilever beam technique and accompanied by structural investigations with atomic force microscopy. Characteristic features in the stress curves provide detailed insight into the development and relief of the misfit strain. For the Stranski–Krastanow system Ge/Si(0 0 1) as well as for SiGe films with Si contents below 20%, the strain relaxation proceeds mainly into two steps: (i) by the formation of 3D islands on top of the Ge wetting layer; (ii) via misfit dislocations in larger 3D islands and upon their percolation.     

Modification of magnetic anisotropy in metallic glasses using high-energy ion beam irradiation

Heavy ion irradiation in the electronic stopping power region induces macroscopic dimensional change in metallic glasses and introduces magnetic anisotropy in some magnetic materials. The present work is on the irradiation study of ferromagnetic metallic glasses, where both dimensional change and modification of magnetic anisotropy are expected. Magnetic anisotropy was measured using Mössbauer spectroscopy of virgin and irradiated Fe₄₀Ni₄₀B₂₀ and Fe₄₀Ni₃₈Mo₄B₁₈ metallic glass ribbons. 90 MeV ¹²⁷I beam was used for the irradiations. Irradiation doses were 5×10¹³ and 7.5×10¹³ ions/cm². The relative intensity ratios D ₂₃ of the second and third lines of the Mössbauer spectra were measured to determine the magnetic anisotropy. The virgin samples of both the materials display in-plane magnetic anisotropy, i.e., the spins are oriented parallel to the ribbon plane. Irradiation is found to cause reduction in magnetic anisotropy. Near-complete randomization of magnetic moments is observed at high irradiation doses. Correlation is found between the residual stresses introduced by ion irradiation and the change in magnetic anisotropy.