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.     

Excitation of localized spatial structures of different symmetry in a system of two thin films

We consider spatial dissipative solitons arising in the system of two nonlinear thin films which interact resonantly with light. Symmetric and nonsymmetric solitons and methods of their exciting and switching are studied.     

Activation of dimethyl zirconocene by methylaluminoxane (MAO)-size estimate for Me-MAO(-) anions by pulsed field-gradient NMR

In a study of the reaction system MAO/(C5H5)2ZrMe2, the size of the ion pair [(C5H5)2Zr(mu-Me)2AlMe2]+ [Me-MAO]- was determined by pulsed field-gradient NMR of its cationic moiety. A mean effective hydrodynamic radius of 12.2-12.5 A, determined from diffusion rates in benzene solution at different zirconocene and MAO concentrations, indicates that the ion pair remains associated even at the lowest concentrations studied. At elevated concentrations, aggregation to ion quadruples or higher aggregates is indicated by an apparent size increase and by shifts of the C5H5 and Me 1H NMR signals. The equilibrium constant for the reaction [(C5H5)2ZrMe+...Me-MAO-] + 1/2Al2Me6 right harpoon over left harpoon [(C5H5)2Zr(mu-Me)2AlMe2]+ [Me-MAO]- changes at different Al/Zr ratios; this indicates that MAO contains various species that produce Me-MAO- anions with different Lewis basicities. The volume of the Me-MAO- anion suggests that it contains 150-200 Al atoms.     

Sulphur electric properties at superhigh pressure around the polymerization temperatures

Abstract

The electrical resistivity temperature dependence of S has been studied in the diamond anvil cell (DAC) of the “rounded cone-plane” type. The pressure is about 50 GPa. The experimental data analysis shows the polymerization between 380–410 K. The electrical resistivity temperature dependence is distorted by a number of maxima, some of them being shifted along the temperature axis towards the lower temperature and disappear with increasing transport current.     

Generation of Extremely Short Pulses upon Excitation of a Resonant Medium by a Superluminal Light Spot

The possibility of generation of quasi-unipolar extremely short pulses (with a duration of several periods of field oscillations) is theoretically analyzed for the excitation of a circular, nonlinear, and resonant medium with a light spot. The light spot rotates along a circle with a velocity that exceeds the speed of light in vacuum, while particles of the medium are distributed uniformly along the circle. It is shown that, by introducing a delay in the form of a phase plate into the system, one can control the shape, the duration, and the amplitude of generated pulses.     

Non-Poissonian statistics in an optical analog of quantum billiard with perfectly square boundaries

We study deviation from the Poissonian statistics of the frequency spacing distribution, appearing due to coupling of polarizational and transverse degrees of freedom in a perfectly square vertical cavity surface emitting laser. The deviation can be controlled by strength of the intracavity anisotropy and its alignment to the device boundaries.     

Generation of an Attosecond Pulse in Helium Excited by Half-Cycle X-Ray Pulses

Optics and Spectroscopy - Conventionally, attosecond pulses are obtained using generation of high-order optical harmonics upon excitation of various media by femtosecond laser pulses with the...     

Generation of unipolar pulses in nonlinear media

Methods recently proposed for generating unipolar pulses in nonlinear media in terahertz and optical electromagnetic ranges are reviewed. Such pulses have nonzero “electric area” (time integral of the field strength over the entire duration of a pulse) and, correspondingly, a significant component of the field with zero frequency, thus exhibiting quasistatic properties. Effective generation of unipolar pulses would allow, e.g., transferring mechanical momentum to charged particles and, thereby, controlling the motion of wave packets of matter, which can be useful for compact accelerators of charged particles and for other applications.     

Ethylene Polymerization in the Presence of Iron(II) 2,6-Bis(imine)pyridine Complex: Structures of Key Intermediates

The structures of intermediates generated by the activation of 2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridineiron(II) chloride (1) with various cocatalysts, methylalumoxane (MAO), trimethylaluminum (TMA), and TMA in combination with B(C₆F₅)₃and Ph₃CB(C₆F₅)₄, is studied by ¹H and ²HNMR spectroscopy. The 1/AlMe₃system exhibits a higher catalytic activity in ethylene polymerization than the 1/MAO system. The activity of the latter decreases sharply with a decrease in the amount of AlMe₃in MAO. Neutral Fe(II) complexes rather than cationic intermediates are suggested to be active components in both catalytic systems.