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961.
RE(III)与2-羰基丙酸水杨酰腙配合物的合成、表征及热化学 总被引:1,自引:0,他引:1
用2-羰基丙酸水杨酰腙与轻稀土硝酸盐反应, 合成了7种新的配合物. 经元素分析、化学分析及X射线粉末衍射等手段确定了其组成为RE(C10H9N2O4)(C10H8N2O4)•nH2O(RE=La、Ce、Pr、Nd、Sm、Eu、Gd), 用红外、紫外、荧光光谱分析对以上配合物的结构进行了表征; 用微热量计测定了稀土芳酰腙配合物的溶解焓, 发现其溶解焓数据不随稀土原子序数单调变化, 而呈转折变化, 可认为呈稀土的四分组现象的前两组. 相似文献
962.
Hanns‐Dieter Amberger Hauke Reddmann Christos Apostolidis Basil Kanellakopulos 《无机化学与普通化学杂志》2003,629(1):147-160
Electronic Structures of Highly Symmetrical Compounds of f Elements. 36 [1] Parametric Analysis of the Optical Spectra of an Oriented Tris(hydrotris(1‐pyrazolyl)borato)praseodymium(III) Single Crystal The absorption and luminescence spectra of polycrystalline tris(hydrotris(1‐pyrazolyl)borato)‐praseodymium(III) (PrTp3) were measured at room temperature as well as at low temperatures. At room temperature the “polarized” luminescence spectra of a small oriented PrTp3 single crystal could also be recorded. On the basis of these spectroscopic findings the underlying crystal field splitting pattern could be derived, and simulated by fitting the free parameters of a phenomenological Hamiltonian, achieving a reduced r.m.s. deviation of 17.3 cm—1 for 37 assignments. On the basis of the parameters used, the global ligand field strength experienced by the Pr3+ central ion as well as the individual ligand field strength associated with one Tp ligand are determined, nephelauxetic and relativistic nephelauxetic effects are estimated, and the experimentally orientiented nonrelativistic and relativistic molecular orbital schemes in the f range are set up. 相似文献
963.
New ternary antimonide Dy3Cu20+xSb11−x (x≈2) was synthesized and its crystal structure was determined by direct methods from X-ray powder diffraction data (diffractometer DRON-3M, CuKα-radiation, RI=6.99%,Rp=12.27%,Rwp=11.55%). The compound crystallizes with the own cubic structure type: space group , Pearson code cF272, . The structure of the Dy3Cu20Sb11−x (x≈2) can be obtained from the structure type BaHg11 by doubling of the lattice parameter and subtraction of 16 atoms. The studied structure was compared with the structures of known compounds, which crystallize in the same space group with similar cell parameters. 相似文献
964.
Haiying Bie Davin G. Piercey Oksana Ya. Zelinska Arthur Mar 《Journal of solid state chemistry》2007,180(8):2216-2224
Investigations on phase relationships and crystal structures have been conducted on several ternary rare-earth titanium antimonide systems. The isothermal cross-sections of the ternary RE-Ti-Sb systems containing a representative early (RE=La) and late rare-earth element (RE=Er) have been constructed at 800 °C. In the La-Ti-Sb system, the previously known compound La3TiSb5 was confirmed and the new compound La2Ti7Sb12 (own type, Cmmm, Z=2, a=10.5446(10) Å, b=20.768(2) Å, and c=4.4344(4) Å) was discovered. In the Er-Ti-Sb system, no ternary compounds were found. The structure of La2Ti7Sb12 consists of a complex arrangement of TiSb6 octahedra and disordered fragments of homoatomic Sb assemblies, generating a three-dimensional framework in which La atoms reside. Other early rare-earth elements (RE=Ce, Pr, Nd) can be substituted in this structure type. Attempts to prepare crystals in these systems through use of a tin flux resulted in the discovery of a new Sn-containing pseudoternary phase RETi3(SnxSb1−x)4 for RE=Nd, Sm (own type, Fmmm, Z=8; a=5.7806(4) Å, b=10.0846(7) Å, and c=24.2260(16) Å for NdTi3(Sn0.1Sb0.9)4; a=5.7590(4) Å, b=10.0686(6) Å, and c=24.1167(14) Å for SmTi3(Sn0.1Sb0.9)4). Its structure consists of double-layer slabs of Ti-centred octahedra stacked alternately with nets of the RE atoms; the Ti atoms are arranged in kagome nets. 相似文献
965.
Nivan B. da Costa Jr. Ricardo O. Freire Gerd B. Rocha Alfredo M. Simas 《Polyhedron》2005,24(18):3046-3051
The sparkle/AM1 model, recently defined for Eu(III), Gd(III) and Tb(III), is now extended to Ho(III). A set of 15 complexes with various representative ligands was chosen by cluster analysis from the set formed by the 27 Ho(III) complexes structures of high crystallographic quality (R factor < 0.05 Å) available in the Cambridge Structural Database and which possess oxygen or nitrogen as coordinating atoms. In the validation procedure, we included the remaining 12 Ho(III) complexes. For these 27 complexes, the Sparkle/AM1 unsigned mean error for all interatomic distances between the Ho(III) ion and the ligand atoms of the first sphere of coordination is 0.05 Å. Sparkle/AM1 constitutes the only semiempirical model for the quantum chemical calculation of Ho(III) coordination compounds available, with geometry prediction accuracies comparable to present day rare earth complex ab initio/ECP calculations, while being hundreds of times faster. 相似文献
966.
It is found that Tb3+ can react with tryptophan (Trp) and sodium dodecyl benzene sulfonate (SDBS), and emits the intrinsic fluoresence of Tb3+. The fluorescence intensity can be enhanced by La3+, Gd3+, Lu3+, Sc3+ and Y3+, among which Gd3+ has the greatest enhancement. This is a new co-luminescence system. The studies indicate that in the Tb-Gd-Trp-SDBS system, there is both Tb-Trp-SDBS and Gd-Trp-SDBS complexes, and they aggregate together and form a large congeries. The fluorescence enhancement of the Tb-Gd-Trp-SDBS system is considered to originate from intramolecular and intermolecular energy transfers, and the energy-insulating sheath effect of Gd-Trp-SDBS complex.Under the optimum conditions, the enhanced intensity of fluorescence is in proportion to the concentration of Trp in the range from 4×10−8 to 4×10−5 mol l−1. The detection limit is 10−9 mol l−1. The proposed method is one of the most sensitive fluoremetries of Trp. 相似文献
967.
The copolymerization of l-octene with styrene catalyzed by rare earth coordination catalysts has been studied for the first time. Some features and kinetic behavior are described. The overall activation energy of the copolymerization was 22.2 KJ/mol and the copolymerization rate could be expressed as R_p=K_p [Nd] [M]~2. (=1.68×10~(-3) L~2/mol~2. S, 50℃, [Oct]/[St]=1). The catalytic activity of various rare earth elements in Ln (naph)_3 for the copolymerization was compared and shows the following sequence: Dy, Y, Yb>Ho>Sm, Gd, Nd>Pr>Ce>La>Tm. Both monomers of l-octene and styrene in the copolymerization by Nd (naph)_3-AlEt_3 have the tendency of constant proportion copolymerization. The structure of the copolymers was studied by ~1H-NMR. 相似文献
968.
The mono- and bisligands complexes formed by rare earth cation (Sc, Y) with pentazolato anion or cyclo-P5− anion, the all-nitrogen counterparts of metallocenes or the all-phosphorus counterparts of metallocenes, have been studied
at hybrid basis sets level with the DFT method. The geometric parameters, binding energy and the charge distributions of these
complexes were characterized. And their stable orders were obtained. Monoligand complexes incline to become bisligands complexes
due to their destabilization. The charge transferring between ligand and metallic cation has affinity with the stability of
complex. The possibility of forming stable [M(η
5-E5)2] (M = Sc, Y, E = N, P) complexes is predicted and they are viable synthetic targets theoretically, especially Sc(η
5-N5)2. 相似文献
969.
Mikhail Ryazanov 《Journal of solid state chemistry》2007,180(4):1372-1380
The title compounds are obtained in high yield from stoichiometric mixtures of Ln, LnI3 and graphite, heated at 900-950 °C in welded Ta containers. The crystal structures of new Pr and Nd phases determined by single-crystal X-ray diffraction are related to those of other Ln12(C2)3I17-type compounds (C 2/c, a=19.610(1) and 19.574(4) Å, b=12.406(2) and 12.393(3) Å, c=19.062(5) and 19.003(5) Å, β=90.45(3)° and 90.41(3)°, for Pr12(C2)3I17 and Nd12(C2)3I17, respectively). All compounds contain infinite zigzag chains of C2-centered metal atom octahedra condensed by edge-sharing into the [tcc]∞ sequence (c=cis, t=trans) and surrounded by edge-bridging iodine atoms as well as by apical iodine atoms that bridge between chains. The polycrystalline Gd12(C2)3I17 sample exhibits semiconducting thermal behavior which is consistent with an ionic formulation (Ln3+)12(C26-)3(I−)17(e−) under the assumption that one extra electron is localized in metal-metal bonding. The magnetization measurements on Nd12(C2)3I17, Gd12(C2)3I17 and Dy12(C2)3I17 indicate the coexistence of competing magnetic interactions leading to spin freezing at Tf=5 K for the Gd phase. The Nd and Dy compounds order antiferromagnetically at TN=25 and 29 K, respectively. For Dy12(C2)3I17, a metamagnetic transition is observed at a critical magnetic field H≈25 kOe. 相似文献
970.
合成了通式为RE(NCS)_3·5DMSO的7种稀土元素异硫氰酸盐与二甲基亚砜的固态配合物(RE=La,Ce,Pr,Nd,Sm,Eu,Gd)。运用本文设计的热化学循环,采用量热法,测定了上述7种配合物在298.15K时的标准生成焓,并计算了它们的晶格能。 相似文献