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71.
Cs3[Tb10(C2)2]Cl21, A New Formula and Structure Type with Isolated Dimeric Clusters Cs3[Tb10(C2)2]Cl21 is obtained via the metallothermic reduction of TbCl3 with caesium in the presence of graphite as black single crystals. The crystal structure (monoclinic, C2/c, Z = 4; a = 2318.72(13); b = 1245.8(9); c = 1502.0(13) pm; β = 98.13(6)°; R = 0.089; Rw = 0.049) contains dimeric clusters that are built from two octahedra connected via one common edge and filled with C2 units. These isolated [Tb10(C2)2] clusters are surrounded by 26 chloride ligands which are then connected via i—a and a—a bridges in a way that voids for Cs+ of coordination number 10 are formed. 相似文献
72.
Caesium heptaiodo‐dititanate(III), CsTi2I7, is obtained from CsI, Ti and TiI4 at 250 °C in a sealed tantalum ampoule as dark red single crystals. The crystal structure (trigonal, R‐3, a = 1706.6(3), c = 2088.3(5) pm, Z = 12, R1 = 0.0619) contains [TiI4] tetrahedra sharing common vertices (with Ti—I—Ti angles of 180°) to isolated ditetrahedra [Ti2I7]—. It may also be described as a cubic closest packing of alternating CsI3 and I4 layers between which neighbouring tetrahedra are occupied in a way that [Ti2I7]— ditetrahedra are achieved. http://www.gerdmeyer.de 相似文献
73.
Gerd Meyer 《无机化学与普通化学杂志》1992,618(12):18-25
CS[Er6C]I12 and cs2Lu[Lu6C]CI18: Examples for Quaternary Reduced Halides of the Lanthanides with Isolated “Clusters” Cs[Er6C]I12 and Cs2Lu[Lu6C]Cl18 were obtained as byproducts through metallothermic reductions of ErI3 and LuCl, with cesium in the presence of carbon in sealed tantalum containers at temperatures ranging from 700 to 940 °C. Cs2Lu[Lu6C]Cl18 (isostructural with Cs2Zr[Zr6H]Cl18, R 3 , a = 981.7 pm, c = 2723.2 pm, Z = 3, R = 0.082, R, = 0.053) contains octahedral [Lu6C] clusters which are slightly compressed along the threefold axis and edge-bridged by twelve chloride anions to form [Lu6C]Cl12 units. Six additional Cl in exo positions of the cluster provide octahedral coordination for the seventh Lu3+. Cs+ occupies anticuboctahedral interstices within the Cl+ layers as a part of the (hexagonal) closest packed arrangement. Cs[Er6C]I12 (trigonal, R 3, a = 1112.0pm, c = 2063.8pm, Z = 3, R = 0.094, R, = 0.068) exhibits [Er6C]I12 units as well and shows the structural framework of Sc[Sc6N]Cl12. Instead of Sc3+ in octahedral holes, cesium occupies a regular iodide position within the ccp sheets forming [CsI3] layers. Both halides are compared with other compounds of the lanthanides containing isolated [M6X12] clusters. The extreme electron deficiency is discussed. 相似文献
74.
Rare‐Earth‐Metal Coordination Polymers: Syntheses and Crystal Structures of Three New Glutarates, [Pr2(Glu)3(H2O)4] · 10.5H2O, [Pr(Glu)(H2O)2]Cl, and [Er(Glu)(GluH)(H2O)2] The new rare‐earth dicarboxylates [Pr2(Glu)3(H2O)4] · 10.5H2O ( 1 ), [Pr(Glu)(H2O)2]Cl ( 2 ) and [Er(Glu)(GluH)(H2O)2] ( 3 ) were obtained from the reactions of glutaric acid with PrCl3·6H2O and Er(OH)3, respectively. The crystal structures were determined by single‐crystal X‐ray diffraction. [Pr2(Glu)3(H2O)4] · 10,5H2O crystallizes in the orthorhombic space group Pnma (no. 62) with a = 871.7(4), b = 3105.0(9), c = 1308.3(9) pm and Z = 4. The crystals of [Pr(Glu)(H2O)2]Cl are monoclinic (I2/a; no. 15) with a = 786.2(1), b = 1527.6(2) c = 801.2(1) pm, β = 99.78(1)° and Z = 4. [Er(Glu)(GluH)(H2O)2] crystallizes in the monoclinic space group P21/a (no. 14) with lattice parameters of a = 882.4(1), b = 1375.3(2), c = 1267.4(2) pm, β = 107.13(1)° and Z = 4. The rare‐earth cations have the coordination numbers 10 ( 1 ), 8 + 1 ( 2 ) and 9 ( 3 ). The individual polyhedra are connected to chains and further to sheets in 1 and 2 and to double chains in 3 . Only in the water‐rich compound 1 there are channels that contain crystal water molecules. It, therefore, has a considerably lower density than 2 and 3 . 相似文献
75.
Ternary Halides of the A3MX6 Type. IV. Ternary Halides of Scandium with Sodium, Na3ScX6 (X = F, Cl, Br): Synthesis, Structures, Ionic Conductivity X-ray studies on single crystals of Na3ScF6 and Na3ScBr6 show, that Na3ScF6 crystallizes with the cryolite type (monoclinic, P21/n, Z = 2, a = 560.16(9), b = 580.31(8), c = 812.1(2)pm, β = 90.720(14)°) and Na3ScBr6, as the only ternary bromide of the rare earth elements with sodium, in the Na3CrCl6 type (trigonal, P3 1c, Z = 2, a = 728.95(7), c = 1309.29(17)pm). The ionic conductivity of powder samples of Na3ScF6, Na3ScBr6 and of Na3ScCl6 was studied by impedance spectroscopy. Activation energies were determined as 1.22 eV, 0.80 eV and 0.71 eV for the fluoride, chloride and bromide, respectively. The differences are explained from the crystal structures and the sizes and polarizabilities of the anions. 相似文献
76.
Gerd Meyer 《无机化学与普通化学杂志》1984,515(8):127-132
CsCu2Cl3 and CsCu2Br3 by Synproportionation at the Metallic Substrate CsCu2Cl3 and CsCu2Br3 are obtained as single crystals via a dry route by synproportionation of mixtures of CsX/2 CuX (X = Cl, Br) and CsCuCl3, respectively, with the copper of the surface of a closed copper cylinder as the metallic substrate. Lattice constants of CsCu2Cl3 (CsCu2Br3) are: a = 950.75(9) (987.3(1)), b = 1189.8(2) (1235.5(2)), c = 559.92(6) (581.80(9)) pm, orthorhombic, Cmcm, Z = 4. Details of the Cs? X polyhedra (X = Cl, Br, I) and the double chains of tetrahedra [Cu2X3]? in CsCu2Cl3, CsCu2Br3, and CsCu2I3 are compared. 相似文献
77.
Two New Silicate-Chlorides with Divalent Europium: LiEu3[SiO4]Cl3 and Li7Eu8[SiO4]4Cl7 LiEu3[SiO4]Cl3 was prepared by reaction of LiCl with Eu2SiO4 and Li7Eu8[SiO4]4Cl7 from Li with Eu2O3, SiO2 and LiCl. The crystal structures of LiEu3[SiO4]Cl3 (Pmna, a = 946.95(13); b = 699.52(8); c = 1 368.0(2) pm; Z = 4; R1 = 0.0325, R2w = 0.0642) and Li7Eu8[SiO4]4Cl7 (P21/c; a = 851.85(5); b = 948.62(7); c = 1 679.0(2) pm; β = 96.221(8)°; Z = 2; R1 = 0.0352, R2w = 0.0744) were determined from four-circle diffractometer data. LiEu3[SiO4]Cl3 contains [Li(SiO4)2] units and LiCl6 octahedra while in Li7Eu8[SiO4]4Cl7 larger ?lithosilicate”? groups are found. In both structures, the Eu2+ ions are coordinated mostly eightfold by O2? and Cl? ligands. 相似文献
78.
Christian Roussel Alexandru T. Balaban Ulf Berg Michel Chanon Roger Gallo Gerd Klatte Joseph A. Memiaghe Jacques Metzger Daniela Oniciu Johanna Pierrot-Sanders 《Tetrahedron》1983,39(24):4209-4219
The effect of the shape of a methyl group on reactivity, which cannot be accounted for by considering a methyl group as a spherical substituent with the appropriate van der Waals radius, was considered in kinetics of alkylalion of substituted pyridines and barriers to rotation and ground state conformations of an isopropyl group attached to a planar framework. The perturbation of a methyl group by an o-methyl group is accounted for by a unique conformational explanation which involves the polyhedral shape of the methyl group. 相似文献
79.
Following an approach to density functional theory calculations based on the matrix representation of operators, we implemented
a scheme as an alternative to traditional grid-based methods. These techniques allow integrals over exchange-correlation operators
to be evaluated through matrix manipulations. Both local and gradient-corrected functionals can be treated in a similar way.
After deriving all the required expressions, selected examples with various functionals are given.
Received: 7 March 1998 / Accepted: 21 May 1998 / Published on line: 6 August 1998 相似文献
80.