Experimental and Theoretical Mechanistic Study on the Thermal Decomposition of 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline

The present paper is a continuation of comprehensive study regarding to synthesis and properties of pyrazoles and their derivatives. In its framework an experimental and theoretical studies of thermal decomposition of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline were performed. It was found, that the decompositions of the mentioned pyrazoline system in the solution and at the melted state proceed via completely different molecular mechanisms. These mechanisms have been explained in the framework of the Molecular Electron Density Theory (MEDT) with the computational level of B3LYP/6-31G(d). A Bonding Evolution Theory (BET) examination of dehydrochlorination of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline permits elucidation of the molecular mechanism. It was found, that on the contrary for most known HCl extrusion processes in solution, this reaction is realised via single-step mechanism.     

On the Moments of Overflow and Freed Carried Traffic for the GI/M/C/0 System

In circuit-switched networks call streams are characterized by their mean and peakedness (two-moment method). The GI/M/C/0 system is used to model a single link, where the GI-stream is determined by fitting moments appropriately. For the moments of the overflow traffic of a GI/M/C/0 system there are efficient numerical algorithms available. However, for the moments of the freed carried traffic, defined as the moments of a virtual link of infinite capacity to which the process of calls accepted by the link (carried arrival process) is virtually directed and where the virtual calls get fresh exponential i.i.d. holding times, only complex numerical algorithms are available. This is the reason why the concept of the freed carried traffic is not used. The main result of this paper is a numerically stable and efficient algorithm for computing the moments of freed carried traffic, in particular an explicit formula for its peakedness. This result offers a unified handling of both overflow and carried traffics in networks. Furthermore, some refined characteristics for the overflow and freed carried streams are derived.     

On one generalization of a DiPerna and Majda theorem

The weak limits of sequences {f(u^ν)}_ν∈? where u^ν's are vector‐valued µ‐measurable functions defined on a compact set Ω and f is (possibly) discontinuous are investigated. As shown by the author (J. Conv. Anal. (to appear)), they are described in terms of integral formulae involving parametrized measures independent of f, similarly as in the classical theorem by Young and its generalization due to DiPerna and Majda. In the present paper we describe the supports of the involved parametrized measures. Copyright © 2006 John Wiley & Sons, Ltd.     

EPR and XPS measurements of polymeric catalysts doped with hereopolyacids in oxygen adsorption studies

The goal of our studies was to determine the nature of interactions between catalytic active samples, such as polypyrrole (PPy) doped with: chloride anions, heteropolyacids such as H₅PMo₁₀V₂O₄₀, or H₄SiW₁₂O₄₀, and oxygen particles. In order to reveal the mechanism of the linkage between the catalysts and oxygen we provided the electron paramagnetic resonance (EPR) measurements of synthesized samples in O₂ and N₂ flow. Moreover, the X-ray photoelectron spectroscopy (XPS) measurements were performed to show the properties of doped heteropolyacids and the state of nitrogen in polypyrrole matrix. The results of EPR studies of PPy(Cl), PPy(H₄SiW₁₂O₄₀), PPy(H₅PMo₁₀V₂O₄₀) samples, show that the polypyrrole doped with chloride anions interacts much easier with oxygen than polypyrrole doped with heteropolyacids (in the above given order, of preference with the most active polypyrrole system first). It correlates with XPS results, which show that a molybdenium-vanadium anion is more reduced than a silicon-tungsten one. The redox reactions of heteropolyacids involve the oxidation-reduction of the conjugated polymer chain, leaving no or little place for interactions with oxygen. Polypyrrole doped with H₄SiW₁₂O₄₀ shows some oxygen sensitivity as observed in the EPR studies, as opposed to polypyrrole doped with H₅PMo₁₀V₂O₄₀, which is in line with the XPS results.     

Exact and approximate results for the Anderson impurity model

This paper provides exact and rigorous upper and lower bounds to the ground state energy of the Single Impurity Anderson Model in the limit of infiniteU. The upper bound approximates the ground state energy very well and the corresponding state may be used as a starting point for further investigations. The energy spectrum of the Single Impurity Anderson Model is calculated exactly for a special non-trivial model density of states describing the bare band electrons. All approaches introduced here are compared to this exact result and to other ground state energy calculations.     

Polysiloxanol condensation and disproportionation in the presence of a superacid

Kinetics studies of the condensation of model hydroxyl-terminated oligosiloxanes, pentamethyldisiloxane-1-ol (MDH) and heptamethyltrisiloxane-1-ol (MD₂H), catalysed by protic complex of tetrakis(pentafluorophenyl)borate in the toluene solution were performed. The dominating reaction was condensation, which was accompanied by disproportionation of oligosiloxanols. Water released in the condensation forms separate dispersed phase, but the phase separation and the presence of water does not affect the rate of the polycondensation. Both processes, condensation and disproportionation, show analogous kinetic laws being first order in silanol and half order in catalyst. They exhibit also similar values of activation parameters. The kinetics are explained by the formation of a reactive protic complex of silanol with borate being in fast preequilibrium with an unreactive complex including two borate molecules and the silanol molecules. The equilibrium lies to the side of the unreactive borate complex.     

Weak boson plus jet production in 2nd-order QCD

We calculate cross sections for the production ofW ⁺ andZ bosons in association with 1 and 2 jets at \(p\bar p\) collider energies. The expected rates for these processes in second-order QCD are presented as a function of the cuts on the transverse momenta of the jets and are compared with jet rates measured by UA1.     

Investigation of the character of the exchange interaction in the system Hg1−xMnxSe

A new method is proposed for determining the magnetic characteristics (magnitude and sign of the exchange interaction energy and the average size of clusters of magnetic ions) of dilute solid solutions of semimagnetic semiconductors at low temperatures based on oscillation measurements. The method makes it possible to find the magnetic characteristics of the indicated systems at temperatures between the point of the transition into the spin glass state and the temperature corresponding to the characteristic binding energy of magnetic atoms in clusters, for which standard methods based on the measurement of the magnetic susceptibility are not effective. The method is used to study the character of the exchange interaction in the system of solid solutions Hg_1–xMn_xSe as a function of their composition as well as under conditions of hydrostatic compression. To this end the oscillations of the magnetoresistance (Shubnikov-de Haas (SH) effect) in single-crystalline samples of Hg_1–xMn_xSe in the region of compositions 0.001 x 0.23 in magnetic fields H up to 65 kOe at temperatures T = (0.4–20) K and pressures up to 16 kbar were studied.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 29–39, November, 1989.