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51.
V. B. Kobychev N. M. Vitkovskaya I. L. Zaitseva B. A. Trofimov 《Journal of Structural Chemistry》2004,45(6):940-944
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. 相似文献
52.
Boris V. L'vov 《Mikrochimica acta》1991,104(1-6):299-308
A basically new mechanism of the thermal decomposition of solids is proposed to explain the mass spectral observations of gaseous molecules of CoO, CuO, Cu2O, NiO, PbO and Mg(OH)2 during the low-temperature decomposition of the anhydrous and hydrated nitrates of these metals. The mechanism consists of two stages: congruent gasification of all reaction products irrespective of their saturated vapor pressure and subsequent condensation of the low-volatility species (oxides and hydroxides). The partial pressures of these species at the appearance temperatures calculated from this theory for the first stage of the process (1–50 mPa) are in agreement with the detection limits of the quadrupole mass spectrometers used in these experiments. The proposed mechanism is supported by other available data obtained by thermal analysis. 相似文献
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55.
采用气相沉积技术在Si衬底上生长了Zn-Zn2SiO4芯-壳结构纳米同轴线阵列。根部呈笋状的纳米同轴线,直径约100nm,长度可以超过10μm;同轴线芯直径约50nm、壳层厚约25nm。通过X射线衍射的表征以及能量色散谱的线扫描,确定纳米同轴线的芯为Zn,壳层为Zn2SiO4。我们提出了一种新的生长机制,同时也为生长均匀的纳米同轴线提供一种新的技术。观察阴极荧光谱发现,纳米同轴线有三个主要发光带:强度最大的中紫外300nm发光、较弱的可见光区560nm以及红外谱区865nm的发光。对纳米同轴线截面的300nm发光峰观测发现,中紫外发光来源于Zn2SiO4壳层。正是这种同轴线的结构,使得其具备特殊的光学性质。 相似文献
56.
Anette Munch Elmr Patric Jannasch 《Journal of polymer science. Part A, Polymer chemistry》2006,44(7):2195-2205
Methacrylate‐functionalized poly(ethylene oxide‐co‐ethylene carbonate) macromonomers were prepared in two steps by the anionic ring‐opening polymerization of ethylene carbonate at 180 °C, with potassium methoxide as the initiator, followed by the reaction of the terminal hydroxyl groups of the polymers with methacryloyl chloride. The molecular weight of the polymer went through a maximum after approximately 45 min of polymerization, and the content of ethylene carbonate units in the polymer decreased with the reaction time. A polymer having a number‐average molecular weight of 2650 g mol?1 and an ethylene carbonate content of 28 mol % was selected and used to prepare a macromonomer, which was subsequently polymerized by UV irradiation in the presence of different concentrations of lithium bis(trifluoromethanesulfonyl)imide salt. The resulting self‐supportive crosslinked polymer electrolyte membranes reached ionic conductivities of 6.3 × 10?6 S cm?1 at 20 °C. The coordination of the lithium ions by both the ether and carbonate oxygens in the polymer structure was indicated by Fourier transform infrared spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2195–2205, 2006 相似文献
57.
We consider a discrete-time stochastic model of an ECN/RED gateway where competing TCP sources share the link capacity. As
the number of competing flows becomes large, the asymptotic queue behavior (normalized by the number of flows) at the gateway
can be described by a simple recursion and the throughput behavior of individual TCP flows becomes asymptotically independent.
A Central Limit Theorem complement is also presented, yielding a more accurate characterization of the asymptotic queue size.
These results suggest a scalable yet accurate model of this complex large-scale stochastic feedback system, and crisply reveal
the sources of queue fluctuations.
This work was prepared through collaborative participation in the Communications and Networks Consortium sponsored by the
U.S. Army Research Laboratory under the Collaborative Technology Alliance Program, Cooperative Agreement DAAD19-01-2-0011.
This work was also supported by the Space and Naval Warfare Systems Center—San Diego under Contract No: N66001-00-C-8063.
The views and conclusions contained in this document are those of the authors and should not be interpreted as representing
the official policies, either expressed or implied, of the Army Research Laboratory or the U.S. Government. 相似文献
58.
R. B. King 《Russian Chemical Bulletin》1993,42(11):1772-1781
Reactions of disodium tetracarbonylferrate, Na2Fe(CO)4, with sterically hindered dialkylaminodichlorophosphines, R2NPCl2 (R2N=diisopropylamino, dicyclohexylamino, and 2,2, 6, 6-tetramethylpiperidino) in diethyl ether lead to the air-stable phosphorus-bridging carbonyl derivatives (R2NP)2COFe2(CO)6 as the major products. The phosphorus-bridging carbonyl group in (i-Pr2NP)2COFe2(CO)6 has been found to undergo the following types of reactions: 1)Reduction, 2)Acylation, 3)Extrusion of the carbonyl group. The mechanisms of the reactions have been considered.This work was presented at the Workshop «The Modern Problems of Heteroorganic Chemistry» held on the ship «Nikolai Bauman» during the period May 8–13, 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1858–1867, November, 1993. 相似文献
59.
Santanu Bhattacharya Basudeb Saha Amitava Dutta Pradyot Banerjee 《Coordination chemistry reviews》1998,170(1):47-74
This review narrates the electron transfer reactions of various nickel(III) and nickel(IV) complexes reported during the period 1981 until today. The reactions have been categorized mainly with respect to the type of nickel complexes. The reactivity of nickel(III) complexes of macrocycles, 2,2′-bipyridyl and 1,10-phenanthroline, peptides and oxime–imine, and of nickel(IV) complexes derived from oxime–imine, oxime and miscellaneous ligands with various organic and inorganic electron donors have been included. Kinetic and mechanistic features associated with such interactions have been duly analyzed. The relevance of Marcus cross-relation equations in the delineation of the electron transfer paths has also been critically discussed. 相似文献
60.