Quantum-Chemical Study of the Profiles of Reactions that Form Pyrrole Anion N-Adducts with CS<Subscript>2</Subscript> and CO<Subscript>2</Subscript>

The profiles of reactions leading to pyrrole anion N-adducts with CO₂ and CS₂ have been studied by the ab initio (RHF/6-31+G*, MP2/6-31+G*) and density functional (B3LYP/6-31+G*) methods. Addition of the pyrrole anion to the carbon disulfide molecule is accompanied by the appearance of a minimum corresponding to a pre-reaction complex. The transformation of the complex to the N-pyrrolyldithiocarboxylate anion occurs via a low activation barrier, which is due to repolarization of the C=S bonds. The profile of the reaction leading to the pyrrole anion N-adduct with CO₂ does not contain any intermediate stationary points throughout the whole route from reagents to products.Original Russian Text Copyright © 2004 by V. B. Kobychev, N. M. Vitkovskaya, I. L. Zaitseva, and B. A. Trofimov__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 990–993, November–December, 2004.     

On the effect of a longitudinal magnetic field on oscillatory characteristics of a subnormal region in discharge in argon

Oscillating nature of current pulses under d.c. excitation in subnormal region with longitudinal magnetic field at pressure range 0.20 torr to 0.85 torr have been studied. The frequency, bandwidth, peak-peak voltage, cut-off current and rise time of the current pulses have been observed with pressure, average tube current and magnetic field. A study of these oscillograms in magnetic field, average tube current and pressure are presented. The probable mechanism for the generation of oscillation based on space-charge field modification with magnetic field is discussed     

Pattern forming precipitation in gels due to coupling of chemical reactions with diffusion

Precipitate-forming chemical reactions have been studied in chemically cross-linked poly(vinyl alcohol) gel medium. One of the reactive components was incorporated into the gel, the other was allowed to diffuse into it. Depending on the experimental conditions the reaction-diffusion process often results in patterns of different type. Experiments performed in tubes and in thin layers were carried out in order to investigate the effects of various factors (cross-linking density, swelling degree as well as the concentrations of the outer and inner electrolytes) on the morphologies of the precipitate patterns. It was found that precipitation occurs not only in the Liesegang bands, but also between bands. Beside Liesegang-type structures, tree-like patterns have been observed, showing a characteristic periodicity in the density profile obtained by digitalized image analyses.     

高灵敏可见／紫外条纹相机的最小可探测能量密度

分析了影响条纹相机最小可探测能量密度的主要因素，通过采用两级增强器级联的方法降低了条纹最小可探测能量密度。利用超短激光脉冲经过标准具后形成一个能量等比衰减的脉冲序列，对ＺＰＴ－３Ｋ紫外／可见皮秒条纹相机的最小可探测能量密度进行了测量。测量表明：相机最小可探测能量密度在可见波段（５３２ｎｍ）达１×１０－１３Ｊ／ｃｍ２。     

高密度氩气的原子间相互作用与状态方程

本文从高密度气体的原子间相互作用出发进行思考,在修改范德瓦耳方程的基础上,提出了一种新的适用于高密度气体的状态方程,并用以对氩气临界区的等温压缩线进行计算,结果与实验值很符合.     

Analysis of Threshold Current and Wall-Plug Efficiency of Diode Lasers with Asymmetric Facet Reflectivity

Threshold current and differential quantum efficiency of broad contact lasers with asymmetric facet reflectivity are discussed with the purpose to reveal factors essential for optimisation of the wall-plug efficiency of such lasers. Lasers with low front facet reflectivity and short cavity often exhibit behaviour difficult to explain with a classical theory. More rigorous calculation performed in this work show that differential quantum efficiency is indeed less affected by a change of the front facet reflectivity or cavity length than predicted by such theory. These findings greatly simplify criteria for optimisation of the wall-plug efficiency of broad contact lasers with coated facets.     

等效法在伏安法测量中的应用

本文提出了在伏安法测量中，消除电表内阻对实验结果影响的一种新方法     

Copolymers containing a spiro orthoester moiety that undergo no shrinkage during cationic crosslinking

A spiro orthoester with an exomethylene group (exoSOE) was radically copolymerized with acrylonitrile or vinyl acetate at several feed ratios to obtain the corresponding copolymers having spiro orthoester moieties in the side chain. The obtained copolymers could be crosslinked via the double ring‐opening polymerization of the spiro orthoester moieties in their side chain by a treatment with BF₃OEt₂. The volume changes upon the crosslinking of the copolymers were evaluated by density measurements with a micromeritics gas pycnometer. The copolymers experienced less than 1% volume expansion instead of volume shrinkage during typical cationic crosslinking, regardless of the copolymer compositions. Negligible shrinkage was observed during the thermal cationic crosslinking of a film cast from a nitrobenzene solution of the copolymers containing a benzylthiophenium salt as a thermally latent cationic initiator. The constantly low volume changes during the crosslinking of the copolymers from exoSOE probably depended on the almost zero volume change during the cationic polymerizations of spiro orthoester derivatives. This indicates that exoSOE is an effective monomer for crosslinkable polymers without volume changes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3666–3673, 2006