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51.
用ab initio能量解析梯度法,在UHF(RHF)/3-21G水平上优化得到AlCn,AlCn+(n=1~3)的四十三个构型,在RHF(UHF)/3-21G水平上优化得到AlC4,AlC4+的二十六个构型,CISD能量.从能量角度所研究的AlCn,AlCn+(n=1~4)构型中,最稳定的构型均是线性构型,且Al全都在端点上,同文献报导的理论和实验结果相一致.此外,还研究了原子簇的离子化能,原子平均结合能以及原子簇的碎片化通道和碎片化能,并计算了上述最稳定构型的谐振动光谱常数. 相似文献
52.
徐灿 《高等学校化学学报》1997,18(6):943-946
利用XeCl准分子激光烧蚀多种硅氧多孔结构材料,在负离子通道测得丰富的「(SiO2)nX」^-负离子团簇,并讨论了多孔网结构和表面活性基团的分布对激光能量的吸收,传输及团簇产生的重要作用。 相似文献
53.
四核钴羰基簇合物Co4(CO)8(μ-CO)2(μ4-PSR)2的合成和晶体结构 总被引:1,自引:0,他引:1
The title compounds Co4(CO)8(μ-CO)2 (μ4-PSR) [R=-CH3, -C2H5, -C(CH3)3,-(CHa)4CH3] were synthesized by the reaction of Co2(CO)8 with RSPCl2. They were characterized by IR, 1HNMR, elemental analysis. The crystal and molecular structure of Co4(Co)8(μ-CO)2 (μ4-PSC2H5) has been determined by single crystal diffraction method. Crystal data: monoclinic, space group P21 /c, with a=8-445(3), 6=8.562(3), c= 17.125(6)Å, β=104.26 (3)' 9 V=1200.1Å3, Z=2, Dc=1.937gcm-3. Its molecular structure contains an octahedral Co4P2 skeleton which consists of a rectangular four cobalt atoms core and the Co4 core is capped above and below by two quadruply bridging PSR ligands. 相似文献
54.
对铝原子簇Al_n(n=1~10,12,13)已报导过的理论预测几何构型进行合理选择, 用量子化学CNDO/2法研究了单分子一氧化碳在这些簇上取不同吸附位形时的吸附作用。结果表明吸附强度随簇尺度的变化呈“幻数”特性: Al_2、Al_6、Al_(12)簇具有特别高的吸附能, 与实验观测结果相符。采用作者建议的推广电子壳模型可合理解释这一尺度效应。对Al_(12)和Al_(13)簇电子结构的分析进一步支持了壳模型的观点。随着簇的增大, 尺度效应逐步减弱并趋向于体相铝的性质。 相似文献
55.
Six new derivatized deltahedral Zintl ions have been synthesized by reactions between the known Zintl ions Ge(9) (n-) with the halides R(3)EX and/or the corresponding anions R(3)E(-) for E=Ge or Sn. This rational approach is based on our previous discovery that these derivatization reactions are based on nucleophilic addition to the clusters. All species were structurally characterized as their salts with potassium countercations sequestered in 2,2,2-crypt or [18]crown-6 ether. The tin-containing anions were characterized also in solutions by (119)Sn NMR spectroscopy. The reaction types for such substitutions and the structures of the new anions are discussed. 相似文献
56.
The oxonium derivative P(C6H5)4[2-B10H9O(CH2)4] (1) has been prepared from [B10H10]2− by a solvent-addition reaction route, promoted by Et2O · BF3. Its structure has been confirmed by single crystal X-ray analysis. 1 is assumed to be a useful synthon for the derivative chemistry of [B10H10]2−. As an illustration, ring-opening reaction occurred in presence of the strong nucleophilic agent OH−, giving the monoanionic derivative [P(C6H5)4]2[2-B10H9O(CH2)4OH] (2). 相似文献
57.
CompoundsformedfromCu ,AgandAuwithdithio lateligands ,suchasthedialkyldithiocarbamate (DTC) ,mercaptothiazoline (HMT)anddialkyldithiophosphates(DDP) ,haveplayedanimportantroleintechnology .1Cu(I) Sclustersalsohavebeenimplicatedinbiologyasan ti oxidants .2Thecuban… 相似文献
58.
Yu. V. Mironov S. F. Solodovnikov V. E. Fedorov Yu. V. Gatilov 《Journal of Structural Chemistry》2004,45(5):874-878
The reaction of a water solution of K4Re6Te8(CN)6 with a solution of Mn(NO3)2 in 0.02M hydrochloric acid in the presence of DMF gave crystals of a cluster rhenium complex [{ Mn(H2O)2(DMF)}2Re6Te8(CN)6]·2H2O. The structure of the compound was determined by single crystal X-ray diffraction (a = 12.6679(9) Å, b = 17.4524(12) Å, c = 9.7882(6) Å, β = 105.570(6)°, V = 2084.6(3) Å3, Z = 2, space group P21/n, R = 0. 0389). In the complex, the [Re6Te8(CN)6]4− cluster anions are linked to Mn2+ cations by the cyanide bridges, the manganese cations being additionally coordinated by the DMF molecule and two water molecules. The neighboring clusters are joined by Re-C-N-Mn bridges into a three-dimensional framework possessing cavities filled with doubly disordered water molecules.Original Russian Text Copyright © 2004 by Yu. V. Mironov, S. F. Solodovnikov, V. E. Fedorov, and Yu. V. Gatilov__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 918–922, September–October, 2004. 相似文献
59.
The static polarizabilities and the second-order hyperpolarizabilities of a series of tri-nuclear metal cluster models MS4(M′PPh3)2(M′PPh3)(M=Mo,W;M′=Cu,Ag,Au)have been calculated within the first-principle theoretical framework. The model clusters have two fragments of rhombic units and it is the charge ransfer from one of these moieties to the other that is responsible for nonlinear optical property. This kind of electronic delocaization, differentiated from that of planar π-system, is very interesting and is worthy for further investigation. 相似文献
60.
David Groswasser Gershon Rosenblum Shammai Speiser 《Journal of photochemistry and photobiology. A, Chemistry》2002,150(1-3):159-165
We have investigated the supersonic jet spectroscopy and photophysics of 1-methylnaphthalene–fluorene (1MN–FL) cluster, and looked for indications of intramolecular electronic energy transfer (Intra-EET) from the FL (donor, D) to 1MN (acceptor, A). The clusters were identified by their time of flight (TOF) mass spectra. We observed clusters bands in the LIF spectrum near the region of 1MN origin. We have also observed cluster TOF–resonance enhanced multi-photon ionization (REMPI) spectrum near the electronic origin of the fluorene moiety. However, this spectrum was almost independent of the excitation wavelength, and was not observed in the LIF spectrum. This is probably due to fast Intra-EET resulting in lifetime broadening of the donor chromophore cluster spectrum, similar to that observed previously for the naphthalene–anthracene bichromophoric system. 相似文献