The mechanism of ethylene polymerization by nickel salicylaldiminato catalysts - Agostic interactions and their kinetic isotope effects

The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (k_H/k_D = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active.     

Thermal gradient induced sidebranching in directional solidification

The polycrystalline perovskitelike manganese oxides La_1-xA_xMnO (A = Na, and K, ) have been fabricated by sol-gel technique. For all the compositions explored in this work, the average manganese oxidation state is practically constant, at for A = Na, and for A = K, respectively. A close relationship is confirmed to hold between the Curie temperature (T_c) and the bond distance of Mn-O. Results of magnetic measurements show that these materials can be utilized as suitable candidates for magnetic refrigerants with wide applied temperature span, for their significant entropy change and the easily tuned Curie temperature. Received: 12 September 1997 / Revised: 18 December 1997 / Accepted: 21 January 1998     

Zeeman效应实验一定能推断出原子的g_J值吗?

本文以实例对Zeeman效应一定能推断原子的gJ值问题做了否定的回答。     

Microwave-assisted, efficient and regioselective Pd-catalyzed C-phenylation of halopyrimidines

We herein report that flash heating microwave irradiation is a helpful tool in the formation of arylpyrimidines from the corresponding halopyrimidines. The palladium-catalyzed cross-coupling reactions of 2,4-di- and 2,4,5-trihalopyrimidines with phenylboronic acid under the above conditions are described. By use of the appropriate catalyst and the adequate halopyrimidine, good regioselectivity can be achieved in the 2-, 4-, or 5-positions of the heterocycle. In addition, we show that this methodology is ameneable for the stepwise preparation of mono-, di-, and triphenylpyrimidines.     

CdSe和ZnO量子点的拉曼光谱研究

本文介绍了用拉曼光谱研究CdSe和ZnO两种Ⅱ Ⅳ族量子点材料的结果,对拉曼峰进行了指认。观察到的光学声子峰位的移动被认为是由量子限制效应引起。     

Stress-Strain State in the Zone of Load Transfer in a Composite Specimen under Uniaxial Tension

The stress-strain state in the zone of load transfer in a uniaxially stretched specimen made of a unidirectional epoxy carbon-fiber-reinforced plastic (CFRP) is investigated. A parametric analysis of the influence of geometric and mechanical characteristics of the specimen on its stress-strain state is performed by means of finite-element modeling. The parameters allowing us to significantly reduce the dangerous concentration of transverse and tangential stresses are revealed. The mechanical tensile characteristics of a high-strength pultruded unidirectional CFRP are determined experimentally, and the size effect of its strength is estimated.     

Influence of transition metal ions on the textural properties of alumina and aluminasilicates

Accelerated phase transformations and chemical reactions of metastable aluminas and kaolinite, doped with Cu^{2 +}, Mn^{3 +}/Mn^{2 +} and Fe^{3 +}/Fe^{2 +} ions, are accompanied with accelerated decrease of surface area and pore volume values. The phenomena in metal ion doped samples are explained by a catalytic mechanism, in terms of the Jahn-Teller effect. This revised version was published online in June 2006 with corrections to the Cover Date.     

Anti-BZ-Structure in Effect Algebras

The definitions of sharply approximating effect algebras, anti-BZ-effect algebras, central approximating effect algebras, and S-anti-BZ-effect algebras are given, the relationships between sharply approximating effect algebras and anti-BZ-effect algebras, between central approximating effect algebras and anti-BZ-effect algebras are established, and the set of anti-BZ-sharp elements in S-anti-BZ-effect algebras is proved to be an orthomodular lattice.     

Photorefractive Four-Wave Mixing Switches Utilizing Pockels Effect -Longitudinal and Lateral Switches-

We carried out detailed calculations for photorefractive wave-mixing switches based on one of three crystals with high electro-optic coefficients, namely, BaTiO₃, Strontium Barium Niobate (SBN (0.75)), and Potasium Sodium Strontium Barium Niobate (KNSBN). A comparison of results for the three crystals shows that a 0_-cut BaTiO³ crystal is suitable for a longitudinal switch and requires a voltage of about 80 for a 2-mm-thick crystal to induce sufficient phase mismatch. The electrodes must be transparent for the incident and diffracted beams. A 45_-cut SBN (0.75) crystal, however, is suitable for a lateral switch and requires a voltage of about 150 for a 1-mm-wide crystal. The electrodes do not need to be transparent.     

Negative luminescence in semiconductors: a retrospective view

Twenty-five years ago, we introduced the phenomenon of negative luminescence (NL) into semiconductor physics. This paper provides an overview of work conducted to develop this fundamental concept. Initially, we consider the first-principle approach to radiation interaction with basic matter and the major properties of NL. Then we describe the problems of NL direct measurements in homogeneous materials and structures. Finally, we emphasize the use of NL approach in applications involving devices for infrared (IR) wavelength (3–12 μm) high-temperature (300–400 K) optoelectronics. Our subjects will include NL IR emitting diodes, radiative coolers, IR dynamic scene simulators, light up-conversion devices, and the Stealth effect in IR.