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21.
J. Escudi C. Couret H. Ranaivonjatovo J. Satge 《Coordination chemistry reviews》1994,130(1-2):427-480
During the last 10 years, several compounds of the type Ge=X (X = C, Ge, N, P, S) have been isolated as monomers. The stabilization of such derivatives, which are generally highly polymerizable, was achieved by using very bulky groups both on the germanium atom and on the heteroelement X. Conjugation (particularly in a few germenes and germaimines) and intramolecular or intermolecular coordination with oxygen or nitrogen, also contributes, in some cases, to the stabilization. The X-ray analyses of such compounds show a significant bond shortening of the double bond (8–10%) relative to the corresponding single bond and a planar or nearly planar germanium. These doubly bonded germanium derivatives are usually thermally stable but must be handled in an inert atmosphere because of their high sensitivity to oxygen and moisture; they are extremely reactive, much more than the corresponding carbon analogues. Nearly quantitative additions on the double bond have been observed with electrophiles and nucleophiles, and various types of cycloadditions also occur. Except in one case, a germylene behavior has not been observed, proving that such compounds retain their structural integrity in solution. 相似文献
22.
To investigate local ordering and segregation phenomenon in a Ni91Pt9-alloy after sputtering and annealing a 3D optical atom probe (OAP) has been used. The specimen tips have been prepared from polycrystalline samples. To sputter the samples a separate preparation chamber with a scannable Ar-sputter-gun is connected to the OAP vessel. When necessary, the sample can be electrically heated to induce segregation and cure the altered layer. After a heat treatment of a Ni91 at. %Pt 9 at.% specimen at 1100 K the surface of a (111)-oriented specimen is enriched in platinum by a factor of two in relation to the bulk. The phenomenon of short-range ordering has been investigated on the surface and in the subsurface volume. A 3D reconstruction of this annealed NiPt specimen shows regions with high concentration of platinum that gives an indication at short-range ordering. Uniform sputtering of the tip without a heat treatment induces a decisive depletion of Pt on the surface and the following subatomic layers. The atom-probe results of specimens in thermal equilibrium are in close agreement to further surface sensitive results obtained from Ion Scattering Spectroscopy (ISS) and Auger Electron Spectroscopy (AES). 相似文献
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24.
A. J. Maroulis P. D. Akrivos C. P. Hadjiantoniou-Maroulis 《Journal of heterocyclic chemistry》1993,30(4):913-916
Oxidation of the title compounds yields, besides the reported isoimides 3 and/or the amides 4 , also the imides 5 . The observed product dichotomy is considered as the result of an intramolecular nucleophilic attack on the aroyl group, of the pressumed zwitterionic intermediate 2 , by O or N present in the ambident N-aroylimine site of 2 . The results of AM1 calculations agree with the product studies and both permit the formulation of a set of rules correlating structure and selectivity. 相似文献
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In this paper, the authors studied certain properties of the estimate of Liang and Krishnaiah (1985, J. Multivariate Anal. 16, 162–172) for multivariate binary density. An alternative shrinkage estimate is also obtained. The above results are generalized to general orthonormal systems. 相似文献
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J. C. Fabris S. V. B. Gonçalves P. E. de Souza 《General Relativity and Gravitation》2002,34(12):2111-2126
The mass power spectrum for a Universe dominated by the Chaplygin gas is evaluated numerically from scales of the order of the Hubble horizon to 100 Mpc. The results are compared with a pure baryonic Universe and a cosmological constant model. In all three cases, the spectrum increases with k, the wavenumber of the perturbations. The slope of the spectrum is higher for the baryonic model and smaller for the cosmological constant model, the Chaplygin gas interpolating these two models. The results are analyzed in terms of the sound velocity of the Chaplygin gas and the moment the Universe begins to accelerate. 相似文献
30.
Allen C. HirshfeldPeter Henselder 《Annals of Physics》2002,302(1):59-77
Deformation quantization, which achieves the passage from classical mechanics to quantum mechanics by the replacement of the pointwise multiplication of functions on phase space by the star product, is a powerful tool for treating systems involving bosonic degrees of freedom, both in quantum mechanics and in quantum field theory. In the present paper we show how these methods may be naturally extended to systems involving fermions. In particular we show how supersymmetric quantum mechanics can be formulated in this approach and consider examples involving both non-relativistic and relativistic systems. 相似文献