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991.
992.
Synthese und Struktur von (NH4)2[(AuI4)(AuI2(μ2-I4))], einem Iodoaurat(III) mit I-Ionen als Liganden
Synthesis and Structure of (NH4)2[(AuI4)(AuI2(μ2-I4))], a Iodoaurate(III) with I42? Anions as Ligands (NH4)2[(AuI4)(AuI2(μ2-I4))] is obtained in a sealed glass ampoule by slow cooling of a mixture of NH4I, Au, and I2 beforehand heated to 500°C. The compound forms black crystals decomposing slowly under loss of I2. It crystallizes in the orthorhombic space group Pnma with a = 1357.7(1), b = 2169.9(2), c = 755.6(3) pm, and Z = 4. The crystal structure is built up by NH cations and square-planar [AuI4]? anions as well as [AuI2(μ2-I4)]? groups being linked together by the I ligands to form chains. The distances Au? I are in the range of 258.7(2) to 262.4(2) pm. The nearly linear I anions are characterized by a short central I? I distance of 270.9(3) pm and two longer outer distances of 338.7(2) pm. 相似文献
993.
Well-resolved absorption spectra of benzoic acid and its derivatives with one hydrogen atom replaced by a substituent group CH3, OH, NH2 or NO2 were reported in the frequency region between 6 and 67 cm^-1 at room temperature with terahertz time-domain spectroscopy (THz-TDS). These substances can be distinguished easily based on the terahertz absorption spectra. The measurements suggested that even minor changes in the molecular configuration and chemical composition lead to distinct differences in THz spectrum. Density functional theory (DFT) method was used to assist the analysis and assignment of the individual THz absorption spectra of benzoic acid and its methyl derivatives. Observed THz responses of samples can be assigned to the collective vibrations associated with intermolecular hydrogen bonds. 相似文献
994.
Hu C Roth A Ellison MK An J Ellis CM Schulz CE Scheidt WR 《Journal of the American Chemical Society》2005,127(15):5675-5688
The synthesis and characterization of six new high-spin deoxymyoglobin models (imidazole(tetraarylporphyrinato)iron(II)) are described. These have been intensively studied by temperature-dependent Mossbauer spectroscopy from 295 to 4.2 K. All complexes show a strong temperature dependence for the quadrupole splitting consistent with low-lying excited states of the same or lower multiplicity. An analysis of the data obtained in applied magnetic fields leads to the assignment of the sign of the quadrupole splitting. All model compounds as well as those of deoxymyoglobin and deoxyhemoglobin, previously studied, have a negative sign for the quadrupole splitting. Although not previously predicted, this experimental observation leads to the assignment of the ground-state electronic configuration for all high-spin imidazole-ligated iron(II) porphyrinates as (d(xz)())(2)(d(yz)())(1)(d(xy)())(1)(d(z)()()2)(1)(d(x)()()2(-)(y)()()2)(1). This is a distinctly different ground-state electronic configuration from other high-spin iron(II) porphyrinates; differences in structural details for the two classes of high-spin complexes are also discussed. The apparent anomaly of differing signs for the zero-field splitting constant between previously studied model complexes and the heme proteins is addressed; the difference appears to result from the fact that the assumptions used in the spin Hamiltonian approach that has been applied to these complexes are not adequately satisfied. Structures of four of the new five-coordinate species have been determined. Core conformations in these derivatives show variation, but these and previously studied compounds reveal a limited number of conformational patterns. The bond lengths and other geometrical parameters such as porphyrin core size and iron out-of-plane displacement support a high-spin state assignment for the iron(II). 相似文献
995.
在具有K2NiF4型结构的Sm2-xSrxNiO4(x=0.4,0.5,0.6,0.8,1.0,1.2,1.4,1.5)化合物上进行了CO催化还原NO的研究。结果表明,低温、低Sr^2+取借代量与高温、高Sr^2+取代量的反应途径不同,这可从化合物的结构、化合物中金属-氧键的标准生成焓的总和、NO还原的表现活化能及化合物上O2的脱附行为等得到解释。 相似文献
996.
Ernesto Schulz Lang Gelson Manzoni de Oliveira Ramo Marceli Fernandes Jr. Ezequiel M. VzquezLpez 《无机化学与普通化学杂志》2004,630(5):717-721
The direct reaction between PhTeCl3 and CsCl in methanol affords {Cs[PhTeCl4]·CH3OH}. Cs[PhTeBr4] was prepared by refluxing [2‐Br‐C5NH5][PhTeBr4] and CsCl in ethanol in the presence of an excess of HBr. In {Cs[PhTeCl4]·CH3OH} the [PhTeCl4]— units form dimers by secondary Te···Cl bonds with methanol molecules bridging adjacent Cs+ cations. In both compounds, the alkali metal cation interacts secondarily with the chlorine and bromine Te‐ligands, achieving singular coordination polyhedrons and holding the lattices in supramolecular tridimensional assemblies. The new complexes, {Cs[PhTeCl4]·CH3OH} and Cs[PhTeBr4], crystallize in the space groups P21/c and P21/n, respectively. Only one such structure has been reported before. 相似文献
997.
Müller-Rösing HC Schulz A Hargittai M 《Journal of the American Chemical Society》2005,127(22):8133-8145
The molecular structure of all silver halide monomers, Ag(2)X, AgX, AgX(2), and AgX(3), (X = F, Cl, Br, I), have been calculated at the B3LYP, MP2, and CCSD(T) levels of theory by using quasirelativistic pseudopotentials for all atoms except fluorine and chlorine. All silver monohalides are stable molecules, while the relative stabilities of the subhalides, dihalides, and trihalides considerably decrease toward the larger halogens. The ground-state structure of all Ag(2)X silver subhalides has C(2)(v)() symmetry, and the molecules can be best described as [Ag(2)](+)X(-). Silver dihalides are linear molecules; AgF(2) has a (2)Sigma(g) ground state, while all of the other silver dihalides have a ground state of (2)Pi(g) symmetry. The potential energy surface (PES) of all silver trihalides has been investigated. Neither of these molecules has a D(3)(h)() symmetric trigonal planar geometry, due to their Jahn-Teller distortion. The minimum energy structure of AgF(3) is a T-shaped structure with C(2)(v)() symmetry. For AgCl(3), AgBr(3), and AgI(3), the global minimum is an L-shaped structure, which lies outside the Jahn-Teller PES. This structure can be considered as a donor-acceptor system, with X(2) acting as donor and AgX as acceptor. Thus, except for AgF(3), in the other three silver trihalides, silver is not present in the formal oxidation state 3. 相似文献
998.
用量子化学从头计算方法研究B_8N_(12)的几何构型、电子结构和振动光谱,讨论其稳定性和化学反应性质。 相似文献
999.
Norbert Schulz 《代数通讯》2013,41(11):1361-1398
1000.