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61.
Pascale F Catti M Damin A Orlando R Saunders VR Dovesi R 《The journal of physical chemistry. B》2005,109(39):18522-18527
The vibrational spectrum of Ca3Fe2Si3O12 andradite is calculated at the Gamma point by using the periodic ab initio CRYSTAL program that adopts an all-electron Gaussian-type basis set and the B3LYP Hamiltonian. The full set of frequencies (17 IR active, 25 Raman active, and 55 inactive modes) is calculated. The effect of the basis set on the calculated frequencies is discussed. The modes are characterized by direct inspection of the eigenvectors and isotopic substitution. The present calculations permit us to clarify some of the assignment problems raised by experiments. The mean absolute differences of the various modes with respect to the available experimental IR and Raman data are as small as 9 and 5 cm(-1), respectively. 相似文献
62.
Pascale F Ugliengo P Civalleri B Orlando R D'Arco P Dovesi R 《The Journal of chemical physics》2004,121(2):1005-1013
The structure of the Si-free katoite hydrogarnet (116 atoms in the unit cell) has been investigated at the periodic ab initio quantum mechanical level with the CRYSTAL program, by using a Gaussian type basis set and both the HF and the hybrid B3-LYP Hamiltonians. The structure has been fully optimized at various pressures in the 0-46 GPa range; the modifications of the structure, and in particular of the (OH)4 group, as a function of pressure are analyzed. At the B3-LYP level and P greater than 15 GPa, a O-H...O interaction of increasing strength appears, with important modifications in the local geometry of the tetrahedral site. The calculated omega01(O-H) fundamental vibrational frequency at zero pressure is in excellent agreement with experiment (3674 and 3663 cm(-1), respectively); the omega01(O-H) stretching frequency remains essentially constant in the 0-15 GPa interval, whereas it dramatically decreases at higher pressures with a corresponding anharmonicity increase, as a consequence of the formation of a strong hydrogen bond. The hydration energy of grossular and the formation energy of Si-free katoite have also been computed, and the B3-LYP results are in quite good agreement with experiment. 相似文献
63.
Le Guennic B Neugebauer J Reiher M Autschbach J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(5):1677-1686
The experimental 13C NMR chemical shift of the central carbon atom in the octahedral [(Ph3PAu)6C]2+ cluster was investigated on the basis of relativistic density functional calculations. In order to arrive at independent model conclusions regarding the value of the chemical shift, a systematic study of the dependence of the cluster structure on the phosphine ligands, the chosen density functionals, and the basis set size was conducted. The best structures obtained were then used in the NMR calculations. Because of the cage-like cluster structure a pronounced deshielding of the central carbon nucleus could have been expected. However, upon comparison with the 13C NMR properties of the related complex [C{Au[P(C6H5)2(p-C6H4NMe2)]}6]2+, Schmidbaur et al. have assigned a signal at delta=135.2 ppm to the interstitial carbon atom. Our calculations confirm this value in the region of the aromatic carbon atoms of the triphenylphosphine ligands. The close-lying signals of the 108 phenyl carbon atoms can explain the difficulties of assigning them experimentally. 相似文献
64.
Nicolas Le Calvez 《中国化学会会志》2002,49(4):585-592
The aim of this study was to develop an analytical method to determine the organochlorine concentrations in sediments. Combination of Microwave assisted Solvent Extraction (MASE) and capillary gas chromatography with specific detection (electron capture detector) was a viable approach for the determination of pesticides in solid matrixes. In this study, MASE development was focused on the selection of a suitable extraction solvent for all the target analytes. MASE procedure was validated by comparison with conventional methods such as Soxhlet and sonication extraction. The proposed method was then applied to determine the organochlorine insecticides concentrations in samples from Authie Bay (France). Environmental water samples were analysed and five target analytes were detected in concentrations from 0.03 to 0.56 ng/g of dry sediment. These investigations showed the accumulation and the persistency of these products in sediments in spite of the fact they were banned a few decades ago. 相似文献
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Summary The existence of a joint asymptotic distribution for the windings of a three-dimensional Brownian motion around a finite number of straight lines is obtained. This complements the recent studies, by Pitman- Yor, and the authors, of the joint asymptotic distribution for the windings of planar Brownian motion around a finite number of points.The following principle governs the passage from results in the plane to results in space:Let B be a three-dimensional Brownian motion, and P
1, ..., P
k, k planes which intersect two by two. Then, the convergences in distribution concerning the planar Brownian motions B
i (1ik), defined respectively as the orthogonal projections of B on P
i (1ik), take place jointly, and the corresponding limit variables are independent. 相似文献
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J. Kuriplach L. Lešták M. Rotter B. Sedlák M. Trhlík M. Finger T. Lešner J. Dupák P. Novák M. Vobecký 《Hyperfine Interactions》1987,34(1-4):339-342
First experimental results of160Tb nuclear orientation in yttrium single crystal matrix are described. The influence of external magnetic field in combination with the crystal field interaction is discussed. 相似文献