Study of microwave pressure lineshifts: Dynamic and isotopic dependences

The study of pressure lineshifts and line broadenings initiated earlier (J. Mol. Spectrosc.94, 264–282 (1982)) is extended to some other perturbing gases and to isotopic species. New dependences of the lineshifts on the molecular parameters are found. One of them is the dependence, as well as the proportionality of the lineshift to the line frequency found before is explained in terms of a “dynamic Stark effect” model. The dependence of the lineshifts on the isotopic composition of the absorbing molecule is also reported. One of the main results of the study is the demonstration of higher sensitivity of lineshifts to the characteristics of molecular interactions as compared to the corresponding line broadening.     

Transition of the near-surface δ layer in an Al/δ(Si)-GaAs tunnel structure to the insulating state under pressure

The tunnel and lateral conductivities of an Al/GaAs tunnel structure with a surface Si δ-doped layer are measured at liquid-helium temperatures under a hydrostatic pressure of up to 3 GPa. Transition of the δ layer to the insulating state at a pressure of about 2 GPa is revealed. During this transition, the tunnel resistance increases steadily (on a logarithmic scale) and the zero-bias anomaly in the tunnel resistance exhibits a sharp peak. These results are interpreted in terms of representations of the effect of pressure on the energy-band structure and behavior of DX levels.     

Polarization-optical and X-ray diffraction investigations on the symmetry of distorted phases of ammonium cryolite (NH4)3 ScF6

Single-crystal plates of different sections of the (NH₄)₃ScF₆ crystal have been investigated by polarization-optical microscopy and X-ray diffraction over a wide temperature range, including the temperatures of two known phase transitions and the third transition found recently. It is established that the symmetry of 5 phases changes in the following sequence: $\begin{gathered} O_h^5 - Fm3m(Z = 4) \leftrightarrow C_{2h}^5 - {{P12_1 } \mathord{\left/ {\vphantom {{P12_1 } {n1}}} \right. \kern-0em} {n1}}(Z = 2) \leftrightarrow C_{2h}^3 - {{I12} \mathord{\left/ {\vphantom {{I12} {m1}}} \right. \kern-0em} {m1}} \\ (Z = 16) \leftrightarrow C_i^1 - I\bar 1(Z = 16) \\ \end{gathered} $ .     

Phase diagrams of Heusler alloys with inversion of the exchange interaction

The phase diagrams of magnetically ordered Heusler alloys with the inversion of the exchange interaction have been studied using the phenomenological Landau theory of phase transitions. It has been shown that the shape of the phase diagrams in these alloys depends on the magnitudes and signs of the phenomenological parameters in the Landau functional. At certain magnitudes and signs of the parameters of the Landau functional, the phase diagrams have thermodynamic paths that allow one to explain the experimentally observed sequences of the phase transitions in the Heusler alloys.     

ECSim2.0 package and simulation of X-ray emulsion chamber experiments

The ECSim 2.0 package is being developed on the basis of the ECSim software package to simulate the development of nuclear-electromagnetic cascades initiated by different particles in a layered medium. Some characteristics of ECSim 2.0 and the results obtained using this package in simulation of the passage of electrons and γ rays through the gamma block of X-ray emulsion chambers in the Pamir Collaboration experiment are discussed. The results obtained are compared with the data of other researchers.     

Highly enantioselective borane reduction of heteroaryl and heterocyclic ketoxime ethers catalyzed by novel spiroborate ester derived from diphenylvalinol: application to the synthesis of nicotine analogues

An asymmetric synthesis for the preparation of nonracemic amines bearing heterocyclic and heteroaromatic rings is described. A variety of important enantiopure thionyl and arylalkyl primary amines were afforded by the borane-mediated enantioselective reduction of O-benzyl ketoximes using 10% of catalyst 10 derived from ( S)-diphenylvalinol and ethylene glycol with excellent enantioselectivity, in up to 99% ee. The optimal condition for the first asymmetric reduction of 3- and 4-pyridyl-derived O-benzyl ketoxime ethers was achieved using 30% of catalytic loading in dioxane at 10 degrees C. ( S)- N-ethylnornicotine ( 3) was also successfully synthesized from the TIPS-protected ( S)-2-amino-2-pyridylethanol in 97% ee.     

Some features of analysis of solutions of fullerenes C60 and C70 by their absorption spectra

The absorption spectra of a series of solutions of C₆₀ and C₇₀ and of their mixture in o-xylene are studied. The deviation from the Bouguer-Lambert-Beer law was observed in the UV absorption band of the solutions. The possible reasons for this effect were analyzed. It is shown that to calculate reliably the composition and concentrations of fullerene mixtures, it is necessary to determine preliminarily the linearity region for the 335-nm absorption band.     

Synthesis and properties of polysiloxane xerogels containing tetrasulfide groups

Polysiloxane xerogels with a functional group content of 1.1?C1.9 mmol/g have been obtained by the hydrolytic condensation of the alkoxysilanes Si(OC₂H₅)₄ and [(C₂H₅O)₃Si(CH₂)₃S₂]₂ in the 2 : 1, 4 : 1, and 8 : 1 ratios. It has been demonstrated by ¹³C and ²⁹Si CPMAS NMR spectroscopy that the xerogels have a polysiloxane framework with dipropyl tetrasulfide bridges, silanol groups, unhydrolyzed ethoxyl groups, and hydrogen-bonded water molecules on the surface. The xerogels have a porous structure. As the molar ratio of the reacting alkoxysilanes is increased in the above-specified range, the specific surface area of the xerogel increases (from 89 to 312 m²/kg) and the same is valid for other structure-adsorption characteristics. The synthesized polysiloxane xerogels readily sorb Hg²⁺ from acidified solutions. Their static sorption capacity can be as high as 1.5 g Hg per gram of sorbent. However, in the course of time, the 1 : 1 complexes forming on the xerogel surface undergo transformations accompanied by the release of mercury sulfide and/or Hg²⁺ reduction to mercury metal.     

Chemical transformations of methane in trifluoroacetic acid

The reaction of methane conversion in anhydrous trifluoroacetic acid (TFA) is shown to take place at room temperature and atmospheric pressure and to result in the formation of a resinous product. Signals of ions with molecular weights of 684 and 700 are observed in MALDI-TOF spectra of the dry residue of methane conversion products.