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In view of immense importance of silylenes and the fact that their properties undergo significant changes on substitution with halogens, here, we have used B3LYP/6-311++G** level of theory to access the effects of 1–4 halogens (X = F, Cl, Br, and I) on four unprecedented sets of cyclopentasilylene-2,4-dienes; with the following formulas: SiC4H3X ( 1 X ), SiC4H2X2 ( 2 X ), SiC4HX3 ( 3 X ), and SiC4X4 ( 4 X ). In going down from F to I, the singlet (s)-triplet (t) energy gap (ΔEs-t, a possible indication of stability), and band gap (ΔEH-L) decrease while nucleophilicity (N), chemical potential (μ), and proton affinity (PA) increase. The overall order of N, μ, and PA for each X is 2 X > 1 X > 3 X > 4 X . Precedence of 2 X over 1 X is attributed to the symmetric cross conjugation in the former. The highest and lowest N are shown by 2 I and 4 F . The trend of divalent angle () for each X is 4 X > 1 X > 3 X > 2 X . The results show that in going from electron withdrawing groups (EWGs) to electron donating groups (EDGs), the ΔEs-t and ΔEH-L decrease while N, μ, and PA increase. Also, rather high N of our scrutinized silylenes may suggest new promising ligands in organometallic chemistry. 相似文献
3.
Matt Visser Carlos Barceló Stefano Liberati 《General Relativity and Gravitation》2002,34(10):1719-1734
Condensed matter systems, such as acoustics in flowing fluids, light in moving dielectrics, or quasiparticles in a moving superfluid, can be used to mimic aspects of general relativity. More precisely these systems (and others) provide experimentally accessible models of curved-space quantum field theory. As such they mimic kinematic aspects of general relativity, though typically they do not mimic the dynamics. Although these analogue models are thereby limited in their ability to duplicate all the effects of Einstein gravity they nevertheless are extremely important—they provide black hole analogues (some of which have already been seen experimentally) and lead to tests of basic principles of curved-space quantum field theory. Currently these tests are still in the realm of gedanken-experiments, but there are plausible candidate models that should lead to laboratory experiments in the not too distant future. 相似文献
4.
固体间界面的物理模型和界面对声波的反射 总被引:4,自引:0,他引:4
简要描述了模拟两固体间界面特性的弹簧模型,该模型最早是根据静力学方法提出的,后来用固体间界面薄层的声波反射方法加以改进,从界面弹簧模型可以方便地得到界面外近似边界条件,其中包含界面“弹簧”振子的劲度常数和质量,文章还给出了两相间固体中界面声反射系数的表达式,介绍了测量界面劲度常数的超声反射谱方法。最后讨论了仍关声波与界面相互作用研究领域中最近的一些研究进展。 相似文献
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采用交流法测量大功率商用钛酸钡(BT)陶瓷加热器的电阻和加热功率随温度的变化关系.结果显示,BT陶瓷的电导特性在80℃附近出现了明显的转变,从低温时的极化子跳跃导电转变为高温时的能带导电,此时,电阻出现极小值,而加热功率出现极大值. 相似文献
7.
本文考虑了选址区域内存在地理阻断情况下的一种基于GIS的选址问题.对单配送中心选址模型,以GIS返回的任意两点间的最短可行路径的长度作为修正距离函数,分析了目标函数在凸形选址区域上非凸非连续的性质.进一步,采用给出了一种近似搜索算法并通过一个实例计算与重心法进行了比较. 相似文献
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Daniel B. Szyld 《Numerical Algorithms》2006,42(3-4):309-323
Given an oblique projector P on a Hilbert space, i.e., an operator satisfying P
2=P, which is neither null nor the identity, it holds that ||P|| = ||I –P||. This useful equality, while not widely-known, has been proven repeatedly in the literature. Many published proofs are reviewed, and simpler ones are presented. 相似文献
10.
A. V. Semykin I. A. Kazarinov E. A. Khomskaya 《Russian Journal of Electrochemistry》2006,42(6):643-648
The hydrogen ionization process is studied experimentally on an industrial sintered nickel oxide electrode in models of sealed nickel-metal hydride batteries. It is shown that the hydrogen ionization rates that are reached during overcharge by high current densities in conditions of forced gas delivery into the electrode pores (up to 40 mA cm?2) exceed the self-discharge rate of a nickel-hydrogen battery by two orders of magnitude. Up to 70% of hydrogen delivered into the compact assembly block undergoes ionization during forced charge of models of sealed nickel-metal hydride batteries with a closed hydrogen cycle. Two independent methods (potentiostatic and manometric) are used to determine the relationship between rates of hydrogen ionization with the degree of the electrode filling with gas and perform estimation of the process intensity at a unit reaction surface. It is established that, in conditions of forced gas delivery, practically all the hydrogen oxidation current is generated at the surface of the nickel oxide electrode beneath thin films of an electrolyte solution at the rate of 4–5 mA cm?2. It is shown that the hydrogen oxidation rate on a nickel oxide electrode filled in part by gas is independent of the electrode potential, probably because of a tangible contribution made by diffusion limitations to the overall hampering of the process. 相似文献