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Kentsch U. Zschornack G. Grossmann F. Ovsyannikov V. P. Ullmann F. 《Hyperfine Interactions》2003,148(1-4):237-242
Hyperfine Interactions - It is well known that many reinforced concrete structures are at risk of deterioration due to chloride ion contamination of the concrete or atmospheric carbon dioxide... 相似文献
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We study the system of nonlinear differential equations which expresses the constancy of the algebraic invariants of the Jacobian matrix for smooth vector fields in three-dimensional space. This system is equivalent to the equations of gas dynamics which describe the barochronous motions of a gas (the pressure and density depend only on the time). We present the results of computation of the admissible local Lie group and construction of the general solution of the system. We mention a few new problems that arise here. 相似文献
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A new procedure for the determination of the heats of thermal gas-phase reversible reactions leading to intermediates in the framework of the adiabatic compression method is proposed. A model problem is solved, and the error of the method is evaluated (-1 %). The validity of the method was confirmed using the reversible formation of the I,2-biradical from tetrafluoroethylene as an example.
Translated from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 64–67, January, 1996. 相似文献
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Andriy B. Zaborovskiy Ruslan E. Prystansky Vitaliy I. Timokhin 《Journal of organometallic chemistry》2004,689(18):2912-2919
The interaction of (Me3Si)3SiH with O2 is known to afford (Me3SiO)2Si(H)SiMe3 in which the two oxygen atoms arise from the same oxygen molecule. In order to investigate the mechanism of this unusual reaction, the oxidation rates were measured in the temperature range 30-70 °C by following oxygen uptake in the presence and absence of hydroquinone as inhibitor. The rate constant for the spontaneous reaction of (Me3Si)3SiH with O2 was determined at 70 °C to be ∼3.5 × 10−5 M−1 s−1. A sequence of the propagation steps is proposed by combining the previous and present experimental findings with some theoretical results obtained at the semiempirical level. These calculations showed that the silylperoxyl radical (Me3Si)3SiOO undergoes three consecutive unimolecular steps to give (Me3SiO)2Si()SiMe3. Evidence has been obtained that the rate determining step is the rearrangement of silylperoxyl radical to a dioxirand-like pentacoordinated silyl radical. Our findings are of considerable importance for the understanding of the oxidation of hydrogen-terminated silicon surfaces. 相似文献
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We review our recent work on the direct calculation of the interfacial free energy, gamma, of the crystal-melt interface via molecular dynamics computer simulation for a number of model systems. The value of gamma as a function of crystal orientation is determined using a thermodynamic integration technique employing moving cleaving walls [Phys. Rev. Lett. 2000, 85, 4751]. The calculation is sufficiently precise to resolve the small anisotropy in gamma, which is crucial in determining the kinetics and morphology of dendritic growth. We report values of gamma for the hard-sphere and Lennard-Jones systems, as well as recent results on the series of inverse-power potentials. For the inverse sixth-, seventh-, and eighth-power systems, we determine gamma for both fcc and bcc crystal structures. For these systems, the bcc-melt gamma is lower than that for fcc crystals by about 25%, consistent with recent experiments and computer simulations on fcc-forming systems that show preferential formation of bcc nuclei in the initial stages of crystallization. In addition, we show that our results give a molecular interpretation of Turnbull's rule, which is the empirical relationship between gamma and the enthalpy of fusion. 相似文献
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Ruslan P. Liferovich 《Journal of solid state chemistry》2004,177(6):2188-2197
Ternary lanthanide scandates (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, and Ho) have been synthesized at ambient pressure. Their structure has been investigated at room temperature by Rietveld analysis of powder X-ray diffraction data. The Ln-scandates are orthorhombic perovskites, adopting space group Pbnm (? 62), a≈b≈√2ap, c≈2ap, Z=4. Heavy lanthanides (Er-Lu), and Y do not form perovskites at ambient conditions. Compositionally driven phase transitions were not observed. The unit-cell parameters decrease with increasing ScO6 octahedron rotation and atomic number of the Ln cation. In common with lanthanide orthoferrites, the uniform structural evolution is interrupted at the middle-heavy part of the lanthanide sequence. This is probably due to an interplay between: (i) enlargement of the ScO6 octahedra relative to BO6 in other perovskites (e.g., FeO6 in GdFeO3); (ii) reduction in size of the first coordination sphere of Ln3+ coincident with the lanthanide contraction; (iii) coincident expansion of the second coordination sphere due to screening effects of OI1 on OI2, and entry of Sc to the lanthanide coordination sphere; (iv) complex mixing between oxygen and lanthanide lanthanide f- and scandium d-orbitals. In the series studied, Ln3+ are in eight-fold coordination (tetragonal antiprism), and are considerably displaced from the center of the LnO8 polyhedron along [001]. Evolution of the crystallochemical characteristics through the Ln orthoscandate series is complex due to both the antipathetic distortions of A- and B-site coordination polyhedra and interaction of the orbitals of oxygen, Ln and Sc. Empirically obtained limits of Goldschmidt and observed viiito tolerance factors for ternary LnBO3 compounds adopting the Pbnm structure are 0.795 and 0.841, respectively. 相似文献