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991.
Ute Ch.?Rodewald Mar’yana?Lukachuk Rolf-Dieter?Hoffmann Rainer?P?ttgenEmail author 《Monatshefte für Chemie / Chemical Monthly》2005,136(12):1985-1991
Summary. The gadolinium–rhodium–indide Gd3Rh1.940(7)In4 was prepared by arc-melting of the elements and subsequent annealing in a corundum crucible in a sealed silica tube. Gd3Rh1.940(7)In4 adopts the hexagonal Lu3Co1.87In4 type, space group
, a = 781.4(5), c = 383.8(3) pm, wR2 = 0.0285, BASF = 0.375(1) (merohedric twinning via a twofold axis (xx0)), 648 F2 values, 22 variables. The structure is derived from the well known ZrNiAl type through an ordering of rhodium and indium
atoms on the Ni2 sites. The Rh/In ordering forces a reduction of the space group symmetry from
to
, leading to merohedric twinning for the investigated crystal. The Rh1 site has an occupancy of only 94.0(7)%. The investigated
crystal had a composition Gd3Rh1.940(7)In4. The main geometrical motif are three types of centered, tricapped trigonal prisms, i.e., [Rh1In26Gd3], [Rh2Gd6In23], and [In1Gd6In23]. The shortest interatomic distances occur for Rh–In (276–296 pm) followed by In–In (297 pm). Together, the rhodium and indium
atoms build up a three-dimensional [Rh1.940(7)In4] network, in which the gadolinium atoms fill slightly distorted pentagonal channels. The crystal chemistry of Gd3Rh1.940(7)In4 is discussed on the basis of a group-subgroup scheme. 相似文献
992.
Yueping?Fang Xiaogang?Wen Shihe?YangEmail author Qi?Pang Lu?Ding Jiannong?Wang Weikun?Ge 《Journal of Sol-Gel Science and Technology》2005,36(2):227-234
Uniform ZnO nanorods arrays are grown directly from and on Zn foils in pure water under hydrothermal conditions at a relatively
low temperature. The nanorods are 80–200 nm in diameter and ∼ 1 μm in length, which grow on the Zn foil along the [001] direction.
By changing the pure water to a urea solution, a Zn compound ([Zn5(OH)6(CO3)2], a precursor of ZnO nanoflowers film, is created by self-assembly. The ZnO nanoflowers film can be easily obtained by heating
the [Zn5(OH)6(CO3)2] compound in N2 at 350∘C for 5–6 hours. Possible growth processes of the ZnO nanorods arrays and the [Zn5(OH)6(CO3)2] nanoflowers are discussed. Photoluminescence properties of the as-prepared ZnO nanostructures have been measured. The ZnO
nanorods array synthesized using our method has minimal defects so that only band-gap emission is observed. However, the ZnO
nanoflowers film, obtained by heating the [Zn5(OH)6(CO3)2] nanoflower precursor in N2, is polycrystalline and displays strong defect-related emission. 相似文献
993.
A dynamics study [cross section and microscopic mechanism versus collision energy (E(T))] of the reaction O+ + H2 --> OH+ + H, which plays an important role in Earth's ionosphere and interstellar chemistry, was conducted using the quasiclassical trajectory method, employing an analytical potential energy surface (PES) recently derived by our group [R. Martinez et al., J. Chem. Phys. 120, 4705 (2004)]. Experimental excitation functions for the title reaction, as well as its isotopic variants with D2 and HD, were near-quantitatively reproduced in the calculations in the very broad collision energy range explored (E(T) = 0.01-6.0 eV). Intramolecular and intermolecular isotopic effects were also examined, yielding data in good agreement with experimental results. The reaction occurs via two microscopic mechanisms (direct and nondirect abstraction). The results were satisfactorily interpreted based on the reaction probability and the maximum impact parameter dependences with E(T), and considering the influence of the collinear [OHH]+ absolute minimum of the PES on the evolution from reactants to products. The agreement between theory and experiment suggests that the reaction mainly occurs through the lowest energy PES and nonadiabatic processes are not very important in the wide collision energy range analyzed. Hence, the PES used to describe this reaction is suitable for both kinetics and dynamics studies. 相似文献
994.
Miguel Clemente-LeónEugenio Coronado José R. Galán-MascarósCarlos Giménez-Saiz Carlos J. Goémez-Garc?&#x;aJean M. Fabre G.A. MousdisG.C. Papavassiliou 《Journal of solid state chemistry》2002,168(2):616-625
The synthesis, structure and physical characterization of three new radical salts formed by the organic donor bis(ethylenediseleno)tetrathiafulvalene (BEDS-TTF or BEST) and the paramagnetic hexacyanoferrate(III) anion [Fe(CN)6]3− or the photochromic nitroprusside anion [Fe(CN)5NO]2− are reported: (BEST)4[Fe(CN)6] (1), (BEST)3[Fe(CN)6]2·H2O (2) and (BEST)2[Fe(CN)5NO] (3). Salts 1 and 3 show a layered structure with alternating organic (β-type packing) and inorganic slabs. Salt 2 shows an original interpenetrated structure probably due to the unprecedented presence of (BEST)2+ dications. The three salts are semiconductors although salt 1 exhibits a high room temperature conductivity and a semiconducting-semiconducting transition at ca. 150 K which has been attributed to a dimerization in the organic sublattice. 相似文献
995.
A closed‐form expression has been derived to obtain the N‐dimensional rectangular atomic wave functions. The wave functions can be obtained straightforwardly with the knowledge of the angular momentum quantum numbers and the dimension and there is no need to employ recursive methods as in previous works. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem 88: 263–274, 2002 相似文献
996.
In ternary aqueous solutions, hydrophobic solutes such as alcohols tend to aggregate with surfactants to form mixed micelles. These systems can be studied by meas of the functions of transfer of hydrophobic solutes from water to aqueous solutions of surfactant. These thermodynamic functions often go through extrema in the critical micellar concentration (CMC) region of the surfactant. A simple model based on interactions between surfactant and hydrophobic solute monomers, on the distribution of the hydrophobic solute between water and the micelles and on the shift in the CMC induced by the hydrophobic solute, can simulate the magnitude and trends of the transfer functions using parameters which are mostly derived from the binary systems. In order to check the model more quantitatively, volumes and heat capacities of transfer of alcohols from water to aqueous solutions of a nonionic surfactant, octyldimethylamine oxide, were measured. A quantitative agreement was achieved with three adjustable parameters. Good fits are also obtained for the transfers to the ionic surfactants, octylamine hydrobromide and sodium dodecylsulfate. When the equilibrium displacement contribution is small, the distribution constants and the partial molar properties of the alcohols in the micellar phase agree well with the parameters obtained with similar models. 相似文献
997.
Monika Moszner Anna M Trzeciak Józef J Zió?kowski 《Journal of molecular catalysis. A, Chemical》1998,130(3):351-248
Rhodium(II) complexes with dioximes [Rh(Hdmg)2(PPh3)]2 [I] (Hdmg=monoanion of dimethylglyoxime) and [Rh(Hdmg)(ClZndmg)(PPh3)]2 [II] catalyse hydroformylation and hydrogenation reactions of 1-hexene at 1 MPa CO/H2 and 0.5 MPa H2 at 353 K, respectively. Hydroformylation with complex [I] produces 94% of aldehydes (n/iso=2.2) and 6% 2-hexene whereas the second catalyst [II] gives ca. 40% of aldehydes (n/iso=2.1) and 60% of 2-hexene. Corresponding Rh(III) complexes are inactive in hydroformylation except of RhH(Hdmg)2(PPh3) [III], which shows activity similar to [I]. Complexes [Rh(Hdmg)2(PPh3)]2 [I], [Rh(Hdmg)(ClZndmg)(PPh3)]2 [II], RhH(Hdmg)2(PPh3) [III] and [Rh(Hdmg)2(PPh3)2]ClO4 [V] catalyse 1-hexene hydrogenation with an average TON ca. 18 cycles/mol [Rh]×min. Complex [II] has also been found to catalyse hydrogenation of cyclohexene, 1,3-cyclohexadiene and styrene. 相似文献
998.
Approaches aiming at eliciting antibodies (Abs) that catalyze specific chemical transformations are numerous. Most of the developed methods are based on the chemical steps of the reaction catalyzed rather than on the structure of known enzyme active sites. The authors have developed an approach that rests on the mimicry properties of the idiotypic network of immune regulation. Recent results, together with the existence of natural catalytic Abs in autoimmune diseases, indicate the need to better understand the regulation properties of immune response, in order to improve the efficiency of tailor-made catalytic Abs. 相似文献
999.
Kenneth Turnbull Thomas L. Blackburn Daniel T. Esterline 《Journal of heterocyclic chemistry》1990,27(5):1259-1263
Bromination of the sydnone ring of several ortho-substituted N-arylsydnones is reported. Subsequent side-chain modification generally can be achieved without concomitant removal of the 4-bromo protective group. 相似文献
1000.
ubica Adam
íková Daniel Miicák Peter ev
ík 《Reaction Kinetics and Catalysis Letters》2005,85(2):215-221
Summary The experimental behavior of the uncatalyzed Belousov - Zhabotinsky reaction between aspirin and bromate in acidic media in the batch reactor has been studied for the first time. Aspirin is an interesting substrate because it is one of the most used medicines. The medical aspirin behaves also in an oscillatory manner with bromate. The oscillating process was investigated under aerobic and anaerobic conditions. The complex dynamic behavior has been observed in the mixed aspirin - vitamin C - BrO3 - H2SO4 system. 相似文献