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31.
Photoirradiation of Os3(CO)10(C14H20) (1) in n-hexane produces the double-decker cluster [Os3(CO)9(C28H40)] [Os3(CO)10] (7), which can also be prepared from the reaction of Os3(CO)9(C28H40) (2) and Os3(CO)10(NCMe)2. Further reaction of 7 with Os3(CO)10(NCMe)2 affords the triple-decker cluster [Os3(CO)9(C28H40)][Os3(CO)10]2 (8). The bis(diyne) complex Os3(CO)8(C14H20)2 (3) reacts with Os3(CO)10(NCMe)2 sequentially to yield the double-decker cluster [Os3(CO)8(C14H20)2][Os3(CO)10] (4) and the triple-decker cluster [Os3(CO)8(C14H20)2][Os3(CO)10]2 (5). Treatment of 3 with Co2(CO)8 at room temperature leads to the mixed-metal triple-decker cluster [Os3(CO)8(C14H20)2][Co2(CO)6]2 (6), while the reaction of 2 and Co2(CO)8 produces [Os3(CO)9(C28H40)][Co2(CO)6]2 (9) and [Os2(CO)6(C28H40)][Co2(CO)6]2 (10). Compound 10, which involves cluster degradation from Os3 to Os2, has been structurally characterized by an X-ray diffraction study. 相似文献
32.
Alistair J Usher Nigel T Lucas Simon Petrie Mark G Humphrey Anthony C Willis 《Journal of organometallic chemistry》2004,689(1):50-57
Reaction of WH(CO)3(η-C5Me5) with IrCl(CO)2(4-H2NC6H4Me) affords WIr3(μ-CO)3(CO)8(η-C5Me5) in low yield. A structural study reveals a WIr2-centred plane of bridging carbonyls, in contrast to the crystal structure of WIr3(CO)11(η-C5H5) (all-terminal carbonyl distribution). DFT calculations reveal an increasing proclivity to adopt an all-terminal CO disposition for clusters MIr3(CO)11(η-C5H5) in the gas phase on proceeding from M=Cr to Mo and then W, consistent with structural studies in the solid state for which the tungsten-containing cluster is the only all-terminal example. Increasing electron donation from the ligands in the tungsten system (either from phosphine substitution or cyclopentadienyl permethylation) suffices to impose a plane of bridging carbonyls in the ground state structure. 13C NMR fluxionality studies reveal that CO exchange mechanism(s) for WIr3(CO)11(η-C5H5) and the related tetrahedral cluster W2Ir2(CO)10(η-C5H5)2 are very fast and involve all carbonyls on the clusters. DFT calculations on MIr3(CO)11(η-C5H5) (M=Cr, Mo) substantiate a ‘merry-go-round’ mechanism for carbonyl scrambling in these systems, a result which is consistent with the scrambling behaviour seen in the NMR fluxionality studies on the W-containing congener. 相似文献
33.
Jürgen Khler Gunnar Svensson Arndt Simon 《Angewandte Chemie (International ed. in English)》1992,31(11):1437-1456
Metal clusters, discrete or condensed, are characteristic of the structures of many compounds which contain transition metals in low oxidation states. The highly reduced oxoniobates support the concept of condensed clusters. They contain Nb6O12 clusters which are either isolated or linked at the apices of the Nb6 octahedra to form oligomeric chains or networks. The analysis of the bonding relationships allows the identification of different types of Nb atoms and thus the quantitative prediction of valence electron concentrations for finite or infinite structures composed of these condensed M6X12 clusters. 相似文献
34.
35.
鲨鱼软骨质量的聚类分析法 总被引:3,自引:0,他引:3
用电感耦合等离子体原子发射光谱法(ICP-AES)测定了18个鲨鱼软骨真品中13个元素含量,对测定结果进行分析和变量聚类分析,抽提5个特征指标,并以谱系数聚类建立了鉴别鲨鱼软骨真伪的数学模式,用3个假冒产品和一个鲨鱼软骨胶囊对其进行检验,结果表明,用无机元素所建立的数学模式不仅能鉴别鲨鱼软骨的真伪,还能区分鲨鱼软骨的部分及不同部位的混合物。 相似文献
36.
37.
Wolfgang A. Herrmann 《Angewandte Chemie (International ed. in English)》1982,21(2):117-130
The Fischer-Tropsch Synthesis counts among the industrial-scale processes having a versatile and broad product range, and has for decades offered the most attractive possibility for the use of coal as a source of heating oil and fuels. This conceivably simple reaction, the catalytic hydrogenation of carbon monoxide, generally leads to simple hydrocarbons as well (i.e. short chain olefins) that have been sought as chemical feedstocks since the oil crisis of the seventies, but fails to provide the large-scale, economic process required, due in large part to the minimal selectivity of traditional Fischer-Tropsch processes. In an effort to solve this problem current research in this sector is concerned not only with the optimization of old and the development of new catalytic systems, but also increasingly with the elucidation of numerous relevant reaction mechanisms. This article will discuss, from the viewpoint of an organometallic chemist, the significance of typical model reactions, both with regard to some fundamental aspects of synthesis gas chemistry, and in comparison with previous views concerning the mechanism of the Fischer-Tropsch Synthesis. The importance of various unique classes of complexes that have been studied in the context of Fischer-Tropsch chemistry is also evaluated with regard to their importance in the synthesis of hydrocarbons from carbon monoxide and hydrogen. It emerges that the primary steps of the reductive oligomerization of carbon monoxide are best described by the carbide/methylene mechanism, as originally proposed by Hans Fischer and Franz Tropsch. 相似文献
38.
《Journal of Pure and Applied Algebra》2022,226(4):106862
We investigate how to characterize subcategories of abelian categories in terms of intrinsic axioms. In particular, we find axioms which characterize generating cogenerating functorially finite subcategories, precluster tilting subcategories, and cluster tilting subcategories of abelian categories. As a consequence we prove that any d-abelian category is equivalent to a d-cluster tilting subcategory of an abelian category, without any assumption on the categories being projectively generated. 相似文献
39.
Pierluigi Contucci 《Journal of statistical physics》1996,82(5-6):1647-1657
We study the coexistence phase in the two-dimensional Ising model. Optimizing the cluster expansion technique, we are able to prove the phase separation phenomenon, with the Onsager value for the surface tension, in a range
, where
estimates from above the critical within 19% and essentially coincides with the entropic bound. 相似文献
40.
The equilibrium geometrical structures of small AlmFen clusters have been determined through ab initio calculation of the cluster total energy at the UB3LYP/Lanl2dz level. For dimers of iron and aluminum, the dissociation energies,
the equilibrium atomic distances, and the vibrational frequencies were calculated. The agreement between calculations and
experiments is reasonable. The ground stable geometrical structures of Fe4, FeAl3, Fe3Al and Fe2Al2 clusters favor three-dimension configurations, but Al4 tetramers are planar structures. The Al-rich tetramers are more stable than the other two composition tetramers. This is
different from that of bulk alloys. 相似文献