Evidence of a Photo‐Radical Pathway Responsible of the Rearrangement of a Manganese(III)‐Schiff Base Complex in Solution

A new Mn^III‐Schiff base complex, [MnL(OH₂)](ClO₄) ( 1 ) (H₂L = N, N′‐bis‐(3‐Br‐5‐Cl‐salicylidene)‐1, 2‐diimino‐2‐methylethane), an inorganic model of the catalytic center (OEC, Oxygen Evolving Complex) in photosystem II (PSII), has been synthesized and characterized by elemental analysis, IR and EPR spectroscopy, mass spectrometry, magnetic susceptibility measurement and the study of its redox properties by cyclic and normal pulse voltammetry. This complex mimics reactivity (showing a relevant photolytic activity), and also some structural characteristics (parallel‐mode Mn^III EPR signal from partially assembled OEC cluster) of the natural OEC. The complex 1 was found to rearrange in solution into a crystallographically solved square‐pyramidal complex, [MnLL′] ( 2 ) (HL′ = 6‐bromo‐4‐chloro‐2‐cyanophenol), through a process, which probably liberates radical species (detected by EPR), and provokes a C—N bond cleavage in the ligand. A photo‐radical mechanism is discussed to explain this rearrangement.     

A representation of the Belavkin equation via Feynman path integrals

 The Belavkin equation, describing the continuous measurement of the position of a quantum particle, is studied. A rigorous representation of its solution by means of an infinite dimensional oscillatory integral (Feynman path integral) defined on the complex Cameron-Martin space is given. Received: 7 January 2002 / Revised version: 20 June 2002 / Published online: 19 December 2002 Mathematics Subject Classification (2000): 81, 81S40, 60H15 Key words or phrases: Belavkin equation – Continuous measurement – Quantum theory – Oscillatory integrals – Feynman path integrals     

Beryllium (boron) clustering quest in relativistic multifragmentation (BECQUEREL Project)

A physical program of irradiation of emulsions in beams of relativistic nuclei named the BECQUEREL Project is reviewed. It is destined to study in detail the processes of relativistic fragmentation of light radioactive and stable nuclei. The expected results would make it possible to answer some topical questions concerning the cluster structure of light nuclei. Owing to the best spatial resolution, the nuclear emulsions would enable one to obtain unique and evident results. The most important irradiations will be performed in the secondary beams of He, Be, B, C, and N radioactive nuclei formed on the basis of JINR Nuclotron beams of stable nuclei. We present results on the charged state topology of relativistic fragmentation of the ¹⁰B nucleus at low energy-momentum transfers as the first step of the research.     

Crystallographic report: A new polymorph for bis[bis(N,N‐dibenzyldithiocarbamato)cadmium(II)]

The title compound is a centrosymmetric dimer with each cadmium in a distorted CdS₅ square pyramidal geometry. The Cd–S bond distances range from 2.5626(11) to 2.8459(11) Å. Copyright © 2004 John Wiley & Sons, Ltd.     

Group Representation of Relativistic Quantum Crystal Optics

A group representation of radiation propagation in an anisotropic medium is developed. The system of wave equations for electromagnetic potentials, obtained from the Maxwell equations with account for the constitutive equations, has been factorized. It is shown that the linear differential operator of the factorized system is orthogonal in transparent crystals and unitary in gyrotropic ones and is represented through the momentum operator. On the basis of the commutation relations for the components of this operator, the eigenvalue problem has been solved and the expression for the change in the radiant energy in the crystal in the form of spherical waves has been obtained. The dependences of the ray and phase velocities and the polarization vectors of waves on the birefringence anisotropy and gyrotropy as well as on the angular momentum, displacement current, and bound charge determining them have been analyzed. It has been established that in the general case of gyrotropic crystals where the nonreciprocity phenomenon takes place and in magnetoelectrics Maxwell equations are represented in a form similar to the Dirac equations and the electromagnetic radiation is correctly described by means of bispinors and is quantized as fermions.     

Fabrication and characterization of a PbTe quantum dots multilayer structure

Multilayer PbTe quantum dots (QDs) and SiO₂ were grown by pulsed laser deposition (PLD) and Plasma enhanced chemical vapor deposition (PECVD) techniques. The crystalline structure, QD size and size dispersion were observed by high-resolution transmission electron microscopy (HRTEM) measurements. This technique allows one to grow PbTe QDs as small as 1.8 nm diameter and 0.6 nm size dispersion. The whole structure can be used in a Fabry–Perot cavity for an optical device operating at the mid-infrared region.     

Liquid-phase noncatalytic butene oxidation with nitrous oxide

The kinetics and mechanism of noncatalytic liquid-phase oxidation of but-1-ene and but-2-ene with nitrous oxide in a benzene solution in the temperature range from 180 to 240°C were studied. Oxidation proceeds via the 1,3-dipolar cycloaddition mechanism to form carbonyl compounds. Both of these reactions occur with close rates and activation energies and have the first orders with respect to the alkene and N₂O. A considerable fraction (39%) of but-1-ene involved in oxidation undergoes cleavage at the double bond yielding propanal and an equivalent amount of methylene, the latter producing ethylcyclopropane and cycloheptatriene. The oxidation of but-2-ene proceeds with a minimum bond cleavage and affords methyl ethyl ketone with 84% selectivity. Regularities of the oxidation of terminal and internal alkenes C₂—C₈ with nitrous oxide were analyzed using the previously published data. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 925–933, April, 2005.     

Numerical approximation of generalized Newtonian fluids using Powell–Sabin–Heindl elements: I. theoretical estimates

In this paper we consider the numerical approximation of steady and unsteady generalized Newtonian fluid flows using divergence free finite elements generated by the Powell–Sabin–Heindl elements. We derive a priori and a posteriori finite element error estimates and prove convergence of the method of successive approximations for the steady flow case. A priori error estimates of unsteady flows are also considered. These results provide a theoretical foundation and supporting numerical studies are to be provided in Part II. Copyright © 2003 John Wiley & Sons, Ltd.