Kinetics of solvolysis of 2-chloroquinoxaline

Pseudo-first-order rate constants and activation parameters have been measured for the solvolysis of 2-chloroquinoxaline in various aquo-organic mixtures using methanol, ethanol, and isopropanol as the organic solvent. Excellent linear correlations are found between lnk and the mol fraction of cosolvent and ln[H₂O]. The medium effect on the rates of solvolysis is assessed by Grunwald–Winstein's mY correlationship. The estimated values of m (0.55–0.72) and the entropy of activation (148–212 J deg^?1 mol^?1) for the reactions are well in the range for a bimolecular aromatic substitution reactions. © 1994 John Wiley & Sons, Inc.     

Does the HO2 radical react with H2S,CH3SH,and CH3SCH3?

The kinetics of the title reactions were investigated in a discharge flow tube by using laser magnetic resonance detection of HO₂. The upper limits for the bimolecular rate constants for the reactions of HO₂ with H₂S (k₁), CH₃SH (k₂), and CH₃SCH₃ (k₃) are <3 × 10^?15, <4 × 10^?15, and <5 × 10^?15 cm³ molecule^?1 s^?1, respectively, at 298 K. Our upper limit for k₁ is three orders of magnitude lower than the previously reported value. Measurements at higher temperatures also yield similar upper limits. Our results suggest that HO₂ is not an important oxidant for these reduced compounds in the atmosphere. © 1994 John Wiley & Sons, Inc.     

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.     

High temperature superconducting thin films for microwave filters

YBa₂Cu₃O_7-δ and Tl₂Ba₂CaCu₂O₈ thin films for microwave filters were synthesized by pulsed laser deposition and the two-step thalliation process. Substrate quality requirements and the relation of thin film morphology, microstructure with microwave surface resistance were discussed.     

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.     

泛连通图定理和Ore2条件

记Ore2=min{d(y) d(x)|x,y∈V(G),d(x,y)=2}，本得到：若n阶图G的Ore2≥n 1，则G是[5;n]泛连通图。此是比Faudree等人的定理进一步的结果。     

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     

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.