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221.
On the basis of the structures and properties of the ClO/ClO? system obtained at the density functional theory (DFT) (UB3LYP) level, employing the 6‐311+G(3df) standard basis set, the electron transfer reactivity of this system is investigated. The results indicate that there are five possible stable coupling complexes that correspond to the generous minima on the global potential energy surfaces (PES). The most stable coupling complex is planar EC4, in which there is a O? O linkage with two trans‐Cl atoms. Their stabilization energies are calculated to be 20.57 (EC1: C1), 20.54 (EC2: C2, 2B), 20.69 (EC3: C1), 20.70 (EC4: Cs, 2A′), and 20.69 (EC.5: C2h, 2Bu) kcal/mol at the B3LYP/6‐311+G(3df) level; with the correction of the basis set superposition error (BSSE), the stability order of these encounter complexes is EC4 > EC.5 > EC3 > EC1 > EC2. Based on the five encounter complexes, five coupling modes are designed for the study of the electron transfer reactivity of this system. The dissociation energy curves at the activated states and the corresponding activation energies of these five coupling modes are obtained and are compared at the B3LYP/6‐311+G(3df) and MP2/6‐311+G* levels. The inapplicability of DFT methods has also been discussed in this article in predicting the energy curves, especially with a long contact distance, in which DFT methods give the abnormal behavior for the dissociations of the complexes caused by the “inverse symmetry breaking” problem. On the basis of the golden rule of the time‐dependent perturbation theory, the electron transfer reactivity and the contact distance dependence of the various electron transfer kinetics parameters (e.g., activation energy, coupling matrix element) have been analyzed at the UMP2(full)/6‐311+G* level. The electron transfer can take place over a range of contact distances, but the most effective coupling distance corresponds to only a small range. The coupling orientation analyses also indicate that the most favorable coupling mode to the electron transfer does not always correspond to the most stable encounter complex mechanism. Some highly energetic coupling modes are more favorable for the electron transfer. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
222.
Torre L. Kenny J. M. Recca A. Siracusa V. Tarzia A. Maffezzoli A. 《Journal of Thermal Analysis and Calorimetry》2000,61(2):565-578
An analysis of the crystallization behaviour of a new poly(aryl-ether-ether-ketone-ketone), PK99, by differential scanning
calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) is presented. Isothermal crystallization TG were obtained in the
whole range between the glass transition temperature (T
g) and the melting temperature (T
m) as a consequence of the slow crystallization kinetics stemming from the closeness of these transitions. The calorimetric
results, compared with WAXD data, were applied to determine the theoretical melting temperature and crystallization enthalpy.
The DSC and WAXD data were combined in order to calculate the total amount of the crystallizable fraction of the polymer,
and a model was proposed to explain the difference between the fractions of crystallinity observed with these techniques.
The thermal and X-ray data were also correlated with different lamellar morphologies arising from the crystallization conditions.
Finally, DSC experiments on the crystallized sample were used to detect the presence of a rigid amorphous phase which does
not relax at T
g.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
223.
对抚州地区秀茶场产的茶叶进行了微量元素测定,提供了五种茶的微量元素谱,同时还对比了秀谷茶场产茶和英德红茶中的微量元素含量的差异。 相似文献
224.
Ostanina T. N. Rudoi V. M. Yaroslavtseva O. V. Solov'ev A. S. Subbotina O. Yu. Dokashenko S. I. 《Russian Journal of Electrochemistry》2004,40(10):1019-1023
The impedance of zinc-rich polymer coatings on steel in a 3-% NaCl solution is studied. The electrochemical behavior of the electrode is satisfactorily described by an equivalent circuit that contains a constant-phase element, which reflects fractal properties of the zinc surface in the binder. From the results of calculations of the circuit elements for metal-rich electrodes with different zinc contents computed are fractions of the active area of the surface of the coating and its fractal dimensionality. 相似文献
225.
Below, we briefly report on the progress in the development of the Filter Diagonalization technique when filtering is carried out with the aid of Finite Fourier Transform (FFT) eigenfunctions. During recent years interest in these functions, also known as ‘prolates’, or ‘slepians’, has increased among scientists doing research in the field of signal processing. The main explanation to this follows from the set of very special extremal and orthogonality properties exibited by the FFT eigenfunctions. Recent results of Walter and Shen on sampling with prolate spheroidal functions will necessary produce a new wave of interest. In the presented, Filter diagonalization machinery, we show that the sampling formula of Walter and Shen simplifies essentially the computation of matrix elements as certain 2D–integrals involving FFT eigenfunctions. 相似文献
226.
报道了以235名健康小儿的血清锌、铜正常参考值及铜/锌比值作依据,对538名本地区集体儿童进行了调查.对240例不同病种患儿的血清锌、铜含量测定,并进行了分析;对G6PD、GSH-PX、AKP醇活性与微量元素含量的关系进行了相关性比较;对微量元素锌缺乏症的患儿进行了临床治疗观察;对微量元素缺乏症的防治进行了讨论. 相似文献
227.
湿热证动物模型微量元素、维生素E变化及清香散的调节作用 总被引:1,自引:0,他引:1
采用多因素造模方法复制成湿热证动物模型,观察了动物模型微量元素Zn、Cu、Fe、Se和维生素E代谢水平的变化。结果显示,模型动物血清Zn下降(P<0.05),Cu升高(P<0.05或P<0.01),Fe变化不大(P>0.05),血Se水平下降(P<0.05),血浆维生素E含量减少(P<0.01)。经清热祛湿的经验方清香散治疗后,治疗I组动物血清Zn、血Se、血浆维生素E明显升高(P<0.05),血清Cu下降(P<0.05);治疗Ⅱ组血浆血清Cu有变化(P<0.05)外,其余变化不大。 相似文献
228.
The concept of the residence time τksp of an atom in a kink site has recently been suggested to understand the processes in electrochemical deposition of alloys
and intermetallic compounds. Different kink sites with different residence times must be defined for alloys and intermetallic
compounds. Based on this model, the finite Markov chain theory is applied to describe the selectivity of the growth process.
An analytical relationship between the alloy composition and the metal ion concentrations in the electrolyte is derived. General
model parameters are ratios g
i = K
ii/K
ij of equilibrium constants of the reaction of electrolyte ions with different kink sites on the surface (i, j representing different alloy components). These ratios are called selectivity constants. For simple conditions, the equation
g
i ≈ τii/τij connects the g
i values with the residence times. The theory is tested in the deposition of alloys Co-Ni (anomalous co-deposition) and Ni-Mo
(induced co-deposition). Additionally, Bi2Te3, an example of stoichiometric semiconductor deposition, is treated.
Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 10, pp. 1216–1223.
The text was submitted by the authors in English. 相似文献
229.
Study of various binding materials like potassium bromide, poly(vinyl alcohol), starch, silver and aluminum has been carried out using laser-induced breakdown spectroscopy (LIBS). The role of matrix effects using these five binders on LIBS signal intensity was investigated for better performance of LIBS technique as a quantitative analytical tool. For comparative study of different binders, the signal intensity of different Mg lines at 518.3, 517.2, 383.8 and 279.5 nm wavelengths were recorded for pellets prepared with known concentrations of Mg in these binders. The influence of laser energy on ablated mass under different binding materials and its correlation with LIBS signal intensity has been explored. Optical scanning microscopy images of the ablated crater were studied to understand the laser ablation process. The study revealed that the binding material plays an important role in the generation of LIBS signal. The relative signal intensity measured for a standard Mg line (at 518.3 nm) were 735, 538, 387, 227 and 130 for potassium bromide, starch, poly(vinyl alcohol), silver and aluminum as binders, respectively. This indicates clearly that potassium bromide is better as a binder for LIBS studies of powder samples. 相似文献
230.
微量元素与防病治病 总被引:8,自引:3,他引:8
宫振沛 《广东微量元素科学》2002,9(12):54-61
介绍了微量元素在防治疾病中的作用及对健康长寿的意义,涉及人体必需微量元素,有害元素,有机锗,微量元素是健康长寿的重要手段以及微量元素与现代文明病。 相似文献