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991.
Marco Häser 《Theoretical chemistry accounts》1993,87(1-2):147-173
Summary A novel formulation of MP2 theory is presented which starts from the Laplace transform MP2 ansatz, and subsequently moves from a molecular orbital (MO) representation to an atomic orbital (AO) representation. Consequently, the new formulation is denoted AO-MP2. As in traditional MP2 approaches electron repulsion integrals still need to be transformed. Strict bounds on the individual MP2 energy contribution of each intermediate four-index quantity allow to screen off numerically insignificant integrals with a single threshold parameter. Implicit in our formulation is a bound to two-particle density matrix elements. For small molecules the computational cost for AO-MP2 calculations is about a factor of 100 higher than for traditional MO-based approaches, but due to screening the computational effort in larger systems will only grow with the fourth power of the size of the system (or less) as is demonstrated both in theory and in application. MP2 calculations on (non-metallic) crystalline systems seem to be a feasible extension of the Laplace transform approach. In large molecules the AO-MP2 ansatz allows massively parallel MP2 calculations without input/output of four-index quantities provided that each processor has in-core memory for a limited number of two-index quantities. Energy gradient formulas for the AO-MP2 approach are derived.Dedicated to Prof. W. Kutzelnigg whose books on theoretical chemistry aroused my interest in this field 相似文献
992.
Structural investigations of thin films of SiC, SiC with free silicon and various titanium suicides (TiSi2, TiSi and Ti5Si3) are described. The crystal phases have been identified using X-ray diffractometry. The growth of reaction products from surface reactions between silicon and deposited titanium can be observed.Dedicated to Professor Dr. rer.nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday 相似文献
993.
In hydraulic high-pressure nebulization (HHPN) an aerosol is produced by means of an HPLC-pump and a special nebulization nozzle, applying a pressure of about 200 bar. This spray technique has been employed for sample introduction of mineral oil samples in flame atomic absorption/flame emission spectrometry. The determination of the trace elements Al, Cr, Cu, Fe, K, Na, Ni, Pb, Si and V has been investigated. Viscosity hardly acts upon the sensitivity of the determination, thereby avoiding a time consuming dilution of oil samples. By means of two interconnecting sampling valves a calibration method based on the standard addition technique can be performed which is both simple and easy to carry out. In samples of used oils, results for Cu and Pb equalled those of XRF-analysis. Regarding Fe traces, data obtained from AAS and XRF measurement correlate. In comparison with sample uptake by pneumatic nebulization, which is restricted to diluted oil samples, detection limits decrease by a factor of 2 to 4, indicating the dilution required in pneumatic nebulization. 相似文献
994.
V. S. Lenenko P. Kränke M. Wahren V. B. Shur M. E. Vol'pin 《Russian Chemical Bulletin》1995,44(7):1293-1299
The interaction of labeled dinitrogen complexescis-(Me2PhP)4Mo(15N2)2 andtrans-(dppe)2W(15N2)2 with non-labeled nitronium and nitrosonium fluoroborates,14NO2BF4 and14NOBF4, in sulfolane at room temperature in the presence of H2SO4 results in rapid formation of labeled nitrous and nitric oxides (15N14NO,15NO), as well as15N14N. The yield of the products depends on the reagent ratio and reaches 10–20 mol. % per mole of a complex under optimum conditions. The mechanism of the reactions found is proposed. It involves the step of protonation of the dinitrogen ligand to form the corresponding hydrazido(2–) derivatives, which are then attacked by nitronium or nitrosonium cations. In accordance with the mechanism proposed, it was established that the hydrazido(2–) complexes, (Me2PhP)3Mo(15N2H2)Cl2 and (dppe)2W(15N2H2)Cl2, are capable of forming15N14NO,15NO, and15N14N under the action of14NO2BF4 and14NOBF4 in the absence of an acid.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 13–13, July, 1995. 相似文献
995.
Oxide ceramic masses react to simple shearing with hardening (peptisation: increase in the shear stress with the shear deformation).
In the present study the correlation between the increase in the shear stress and the porosity, agglomeration processes and
the type of flow are analysed. For this purpose oxide ceramic masses are tested in a shear device especially developed for
pastes and analysed by rheometric experiments, NMR methods and particle size analysis. The results support the hypothesis
that structural changes (hardening, increase in the mean porosity) of the material during the peptisation mainly depend on
the magnitude and not on the kind of the energy input and thus of the type of flow. The fraction of bound (more generally,
the immobilised) water increases with the shear displacement. Also crushing of primary particles could be observed. Both the
crushing of solid particles causing an increased solid surface and the formation of a three-dimensional gel structure are
microscopic effects capable of resulting in the binding or retaining water. On a macroscopic scale these phenomena cause hardening.
Magnetic resonance imaging visualises flow-induced agglomerates, which form owing to the shear flow and increase the porosity
averaged over the whole sample. After the shear experiment rolls of paste can be seen which indicate that the general assumption
of a plane shear flow in the shear device is not warrantable.
Received: 19 July 2001 Accepted: 25 October 2001 相似文献
996.
Ingomar Jäger 《Mikrochimica acta》1981,76(5-6):447-455
Zusammenfassung Die zeitliche Entwicklung der Mikrorauhigkeit einer Oberfläche während des Sputterns wurde für verschiedene Größen der Oberflächendiffusionskoeffizienten untersucht. Das Modell berücksichtigt die Bedeckungsgradabhängigkeit der Diffusionsweglänge. Effekte der Korrelation zwischen Atomen beim Sputtern wurden diskutiert. Es wurde gezeigt, daß ab einem Schwellenwert des Oberflächendiffusionskoeffizienten die Tiefenauflösung nahezu konstant wird, statt mit der Quadratwurzel der Sputtertiefen anzuwachsen.
Vorgetragen beim 10. Kolloquium über metallkundliche Analyse, Wien, 3.-5. November 1980. -Herrn Prof. Dr. Hanns Malissa zum 60. Geburtstag gewidmet. 相似文献
The development of surface roughness during sputtering
Summary The time-dependence of the micro roughness of a surface during sputtering is investigated for various values of the coefficient of surface diffusionD s using a model of a coverage dependent diffusion length. Effects of correlation between atoms within the sputtered layer are discussed. It is shown that beginning at a threshold value ofD s the depth resolution of sputtering becomes a constant instead of being proportional to the square root of the sputter depth.
Vorgetragen beim 10. Kolloquium über metallkundliche Analyse, Wien, 3.-5. November 1980. -Herrn Prof. Dr. Hanns Malissa zum 60. Geburtstag gewidmet. 相似文献
997.
Sharp peaks were observed in the IR spectra of allyl alcohol dimers in the νOH and τOH regions in low-temperature Ar and N2 matrices. In Ar a peak at 3587 cm?1 was found to increase in intensity upon annealing and decrease upon IR irradiation; it is concluded that this peak is due to an OH...π interaction (of a cyclic structure) present in part of the dimers. This is the first time such an interaction and photoprocess have been found for an alcohol in matrices. Also a faster photo-process was found. Confomer changes in the monomers accompany the photoprocess in allyl alcohol dimers. 相似文献
998.
Equations between the differential order and the maximum of the fractional-order differential for the specified peak signals are developed based on the variation of the maximum of the specified peak signals at different orders. Also, equations between the differential order and the zero-crossing of the fractional-order differential of the specified peak signals are proposed according to the variation of the zero-crossing of the specified peak signals at different orders. Characteristic paramters of the Gaus- sian peak, Lorentzian peak, and Tsallis peak can be estimated using estimator I and estimator II which are obtained by the equations above. As a result, a new method is presented to resolve the overlapped peaks signal. Firstly, a fractional-order differential of the specified peak signals is obtained with the fractional-order differentiation filter. Then, characteristic paramters of the specified peak signals can be extracted using estimator I and estimator II. Finally, the Tsallis peak is used as a model to assign the overlapping peak signals correctly. Experimental results show that the proposed method is efficient and effective for the simulated overlapping peaks and detected overlapping voltammetric peak signals. 相似文献
999.
To obtain new materials with synergetic or complementary behaviors, polyaniline composite filled with ZnO rods in ramification-like
structure was prepared by a hydrothermal approach. Comparative experiments of ZnO preparation in the presence of some metal
ions were also carried out. The results indicated that the morphology of ZnO was strongly affected by the preparation condition.
The method to grow ZnO rods in the presence of polyaniline offers a simple approach to obtain polyaniline composite filled
with linear ZnO structure. The results of X-ray photoelectron spectroscopy show that the strong interaction between ZnO and
polyaniline possibly exists to cause the charge transfer. 相似文献
1000.
Kayed A. Abu Safieh Ahmad M. Abu Mahthieh Mustafa M. El-Abadelah Mikdad T. Ayoub Wolfgang Voelter 《Monatshefte für Chemie / Chemical Monthly》2007,138(2):157-160
Summary. A novel method for the synthesis of a new series of 5-substituted 1,3-dimethyl pyrazolo[4,3-e][1,2,4]triazines is described. The new synthetic strategy is based on the classical Bischler 1,2,4-benzotriazine synthesis. This approach involves the preparation of 5-hydrazinopyrazole from 5-chloro-1,3-dimethyl-4-nitropyrazole
followed by acylation and nitro group reduction to form the corresponding 4-amino-3-(acylhydrazino)pyrazoles. Intramolecular
oxidative cyclization of the latter derivatives, using polyphosphoric acid, produced the respective target pyrazolotriazines. 相似文献