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41.
Beitone L Marrot J Loiseau T Férey G Henry M Huguenard C Gansmuller A Taulelle F 《Journal of the American Chemical Society》2003,125(7):1912-1922
A new fluorinated gallium phosphate, MIL-50, has been synthesized under mild hydrothermal conditions using 1,6-diaminohexane. The chemical formula of MIL-50 is Rb(2)Ga(9)(PO(4))(8)(HPO(4))(OH)F(6).2N(2)C(6)H(18).7H(2)O. The structure is a network of hexameric units of Ga(3)(PO(4))(3)F(2) and Ga(3)(PO(4))(2)(HPO(4))F(3) via corner sharing. It creates a three-dimensional open-framework delimiting 6- and 18-ring channels running along the c axis. The diprotonated 1,6-diaminohexane and water molecules are trapped within the 18-ring pores, whereas the rubidium cations reside in the 6-ring ones. A double quantum (31)P NMR experiment and partial charge calculations indicate that water molecules are present under the form of periodic small clusters, lowering the multiplicity of one phosphorus site, P3. Though water hops within the clusters, the motion leaves the water pattern periodic. Rubidium is so tightly embedded into the framework that water moving in the large 18-ring channels does not reach it, leaving it therefore dry. The crystal framework may be ascribed to the orthorhombic space group Cmc2(1) (n degrees 36), a = 32.1510(2), b = 17.2290(3), c = 10.2120(1) A. The periodic water pattern has a different symmetry than that of the framework. A method has been devised to superpose the two sublattices that coexist in the same unit cell in order to have full occupancy of each site and to perform Madelung summations. This original method is of general interest for most zeolitic materials exhibiting a different symmetry for the framework and the template sublattices. 相似文献
42.
Dr. Theodor N. Kleinert Dr. Roderick E. Townshend 《Monatshefte für Chemie / Chemical Monthly》1970,101(2):375-379
Zusammenfassung Die beim Verstrecken sowie Mahlen von künstlichen organischen Fasermaterialien (Polyester-, Polyamid- und Viskosefasern) als Folge homolytischer Kettenspaltungen auftretende Freiradikalbildung wurde untersucht.
Mit 3 Abbildungen
Die Elektronspinresonanz-Messungen wurden im Chemischen Institut der Sir George Williams University, Montreal, Canada, durchgeführt. 相似文献
Mechanochemical reactions in synthetic organic fibres
The formation of free radicals due to homolytic chain fission occurring in the course of stretching and grinding of synthetic organic fibres (polyester, polyamide, and viscose fibres) has been investigated by means of ESR spectroscopy.
Mit 3 Abbildungen
Die Elektronspinresonanz-Messungen wurden im Chemischen Institut der Sir George Williams University, Montreal, Canada, durchgeführt. 相似文献
43.
Under the assumptions thatq is not a root of unity and that the differentialsdu
j
i
of the matrix entries span the left module of first order forms, we classify bicovariant differential calculi on quantum groupsA
n–1
,B
n
,C
n
andD
n
. We prove that apart one dimensional differential calculi and from finitely many values ofq, there are precisely2n such calculi on the quantum groupA
n–1
=SL
q
(n) forn3. All these calculi have the dimensionn
2. For the quantum groupsB
n
,C
n
andD
n
we show that except for finitely manyq there exist precisely twoN
2-dimensional bicovariant calculi forN3, whereN=2n+1 forB
n
andN=2n forC
n
,D
n
. The structure of these calculi is explicitly described and the corresponding ad-invariant right ideals of ker are determined. In the limitq1 two of the 2n calculi forA
n–1
and one of the two calculi forB
n
,C
n
andD
n
contain the ordinary classical differential calculus on the corresponding Lie group as a quotient. 相似文献
44.
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46.
47.
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48.
49.
Becke AD 《The Journal of chemical physics》2005,122(6):064101
Real-space models of nondynamical correlation between electrons of opposite spin and of parallel spin in multicenter (molecular) systems are discussed. These models are designed to be partnered with Hartree-Fock or exact Kohn-Sham exchange. Thus the numerous and well-known problems of local density-functional exchange-correlation approximations, especially in stretched odd-electron systems, are circumvented. 相似文献
50.
A recent exact-exchange-based density-functional model of nondynamical and dynamical correlation [A.D. Becke, J. Chem. Phys. 122, 064101 (2005)] is tested on 70 barrier heights for a variety of reaction types: hydrogen transfer reactions, heavy-atom transfer reactions, nucleophilic substitutions, association reactions, and unimolecular rearrangements, including both even- and odd-electron systems. The mean absolute error with respect to accurate reference data is 1.4 kcal/mol. This is achieved without any refitting of the parameters of the model to the barrier height data. 相似文献