高硅沸石骨架结构及其稳定性的模拟计算(I)*

The lattice energy of a series of high-silica zeolites was determined using the lattice energy minimization method. The results were compared to the lattice energy of dense polymorphs of SiO2. All high-silica zeolites frameworks are only 30～67kJ•mol-1 less stable than α-quartz This may imply that there is little energy barrier to the formation of high-silica zeolites frame-works and explain the structural diversity observed for high-silica zeolites. The relationships of calculated lattice energies and framework Structures was disscussed. The results revealed a good linear relationship between framework density of these molecular sieves and all-silica framework lattice energies.     

Lithium insertion into In2S3 studied by perturbed γ-γ angular correlation

Li_xIn₂S₃ was electrochemically prepared with different small amounts x of lithium (0?x?0.13) in order to maintain the initial crystallographic structure of the thiospinel In₂S₃. About 10¹² radioactive ¹¹¹In ions have been implanted into these samples at 400 keV to perform PAC experiments in the temperature range from 10 to 773 K. The results are compared to previous experiments with undoped In₂S₃ samples. According to the structure of In₂S₃ in the β-phase, which belongs to the I4₁/amd space group having a unit cell with 32 In and 48 S atoms and the cell parameters α=7.61 Å and c=32.28 Å, three different electric field gradients were observed. Within two different temperature ranges dynamical EFGs occur, which are clearly influenced by the insertion of Lithium. The strong dependence of one EFG on the Li concentration x can be correlated to the effective charge of the In ions. This correlation is discussed with respect to XRD analyses of the Li_xIn₂S₃ samples and to XANES measurements on a similar sample.     

Oxidation products of the niobium tungsten oxide Nb4W13O47: A high-resolution scanning transmission electron microscopy study

Nb₄W₁₃O₄₇, a member of the solid solution series Nb_8−nW_9+nO₄₇ (0?n?5), crystallizes in a threefold superstructure of the tetragonal tungsten bronze structure. While the oxidation of this reduced phase at T_OX=1200 °C leads to a separation into the thermodynamically stable phases, lower oxidation temperatures result in products that comprise new structural elements and ordering variants. The characterization of the oxidation products obtained at T_OX=1000 °C was performed by scanning transmission electron microscopy applying a high-angle annular dark field detector. At the selected imaging conditions (Z contrast), not only the metal positions are revealed by this technique but valuable additional information about the elemental distribution can be obtained simultaneously.     

Unexpected solids from enantiopure cationic palladium complexes and racemic anions: A structural study of chiral non-discrimination

Enantiomerically pure cationic complexes were obtained via cyclopalladation of primary amines and subsequent addition of a chelating ethylendiamine ligand. No diastereomeric resolution was observed upon combining these cations with racemic mandelate or hydratropate anions, but four less popular products, namely three double salts and a solid solution, were obtained and structurally characterized. For one of the double salts, the alternative ionic compounds based on different stereoisomers of the same residues were synthesized independently: The conventional racemic solid and both diastereomeric salts formed by enantiopure cations and anions were studied by single crystal X-ray diffraction. Lattice energy calculations confirm that the diastereomeric salts differ significantly; formation of the partially racemic double salt, however, is energetically favourable and precludes resolution.     

Application of coset representations to the construction of symmetry adapted functions

Summary A coset representation (G(/G _i )), which is defined algebraically by a coset decomposition of a finite groupG by its subgroupG _i , is shown to be a method for the decomposition of a regular body into its point group orbits. This proof also shows that each member of theG(/G _i ) orbit belongs to theG _i site-symmetry. In addition, a general equation concerning the multiplicities of such coset representations is derived and shown to involve Brester's equations and thek-value equations of framework groups as special cases. The relationship of the coset representation and the site-symmetry affords a general procedure for obtaining symmetry adapted functions.     

Repleteness and regular lattice measures

Let X be an abstract set and L a lattice of subsets of X. To each lattice regular measure µ, we associate two induced measures and on suitable lattices of the Wallman space IR(L) and another measure µ on the spaceIR(L). We will investigate the reflection of smoothness properties of p onto , and µ; and try to set some new criterion for repleteness and measure repleteness.     

Surface properties of the binary mixed systems of alkylpyridinium halides and sodium alkylsulfonates

Surface properties of the binary mixed systems of decyl- and dodecylpyridinium chloride or bromide and sodium pentyl- and heptylsulfonate have been investigated. The surface tension of solutions of equimolar mixtures of surfactants and individual surfactants was measured, and the composition of mixed monolayers and surface interaction parameter β were calculated with the regular solution theory. Our results indicate that the properties of mixed films depend on both ionic strength and the kind of added inorganic electrolyte. With the increase of inorganic electrolyte concentration, the content of more surface active ions in the adsorption films enhances and is the highest in the presence of NaI and the smallest when solutions contain NaCl. Mutual interactions in mixed adsorbed films were found to be attractive. However, the strength of interaction weakens with the increase of ionic strength and depends on the kind of inorganic ions in the order: Cl⁻>Br⁻>I⁻.     

Noether's Theorem on Surfaces

In this article we prove a version of Noether's Theorem (of Calculus of Variations) which is valid for a general regular (compact) surface. As a special feature, the Lie group of transformations is allowed to act on the Cartesian product of the surface and the functional space. Additionally, we apply the Theorem to a problem in Classical Differential Geometry of surfaces. The given application is actually an example showing how Noether's Theorem can be used to construct invariant properties of the solutions to variational problems defined on surfaces, or equivalently, of the solutions to the associated Euler-Lagrange equations resulting from them.     

Permeability of microscale fibrous porous media using the lattice Boltzmann method

The permeabilities of microscale fibrous porous media were calculated using the multiple-relaxation-time (MRT) lattice Boltzmann method (LBM). Two models of the microscale fibrous porous media were constructed based on overlapping fibers (simple cubic, body-centered cubic). Arranging the fibers in skew positions yielded two additional models comprising non-overlapping fibers (skewed simple cubic, skewed body-centered cubic). As the fiber diameter increased, the fibers acted as granular inclusions. The effects of the overlapping fibers on the media permeability were investigated. The overlapping fibers yielded permeability values that were a factor of 2.5 larger than those obtained from non-overlapping fibers, but the effects of the fiber arrangement were negligible. Two correlations were obtained for the overlapping and non-overlapping fiber models, respectively. The effects of the rarefaction and slip flow are also discussed. As the Knudsen number increased, the dimensionless permeability increased; however, the increase differed depending on the fiber arrangement. In the slip flow regime, the fiber arrangement inside the porous media became an important factor.