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71.
采用第一性原理的计算方法,在不同条件下对Heusler型X2RuPb(X=Lu,Y)体系的电子结构展开研究.计算结果表明,这些合金在适当晶格变形或掺杂条件下,能够具有真正的拓扑绝缘体特性.杂化作用和自旋-轨道耦合作用都对材料产生"反带"结构发挥作用.但是针对不同成分所构成的材料,它们各自所起作用的程度有所不同,二者可以相辅相成.利用替换掺杂和四角变形双重调控方式可以更理想地进行"反带"结构调控进而获得理想的拓扑绝缘体,这对于材料的实际制备具有重要意义. 相似文献
72.
The thermal properties and thermal stability of diaspore-corundum (AlOOH-Al2O3), from Goian (Pontevedra, Spain) were studied by means of differential thermal analysis (DTA), thermogravimetry (TG), high temperature X-ray diffraction (HTXRD) and thermally stimulated luminescence (TL) techniques. The samples were annealed to link the combined effect of (i) dehydroxylation, (ii) oxidation-reduction of chromophores (Mn 0.5%, Fe2O3 0.12%, TiO2 0.021% and Cr 80 ppm) determined by inductively coupled plasma-atomic emission spectrometry (ICP-AES) and (iii) phase transitions whilst sample heating (i.e. α-AlOOH→α′-Al2P3→α-Al2O3). The blue colour of diaspore, attributed to the Ti4+-Fe2+ intervalence-charge-transfer mechanism, turns to white (circa 500 °C) in good agreement with the DTA endothermic peak (dehydroxylation). The coexistence of α-AlOOH and α′-Al2P3 phases has been detected by in situ HTXRD and could be correlated to the thermoluminescence tests performed on preheated aliquots (up to 500 °C). 相似文献
73.
L.M. da Silva M.C. de Melo A.N. Medina F.G. Gandra 《Physica B: Condensed Matter》2009,404(19):3018-3020
We report on results of X-ray powder diffraction, magnetization and specific heat measurements of the pseudo-ternary (Ce1−xLax)PdIn2 system with x=0; 0.2; 0.4 and 0.6. The results show a linear increase of the unit cell volume and a reduction of the ferromagnetic transition as La content increases. The Debye temperature, Sommerfeld coefficient and crystal field parameters were estimated from specific heat data, and are found to be weakly dependent of the Ce concentration. Also, the variation of magnetic entropy at TC is only weakly dependent on x (ΔS≅0.92Rln2) indicating that TK/TC is approximately constant along the series. The TC and TK behaviors are explained by the variation of the exchange parameter due to the volume change when Ce is replaced by La. Our results indicate that the chemical pressure is the dominant effect rather than the chemical disorder for determining the physical proprieties of the (Ce1−xLax)PdIn2 system. 相似文献
74.
From a new magnetically diluted spinel oxide with composition Fe0.6Mg1.6Ni0.1Ti0.7O4 an as-prepared sample and one after reheating three times have been investigated with Mössbauer spectroscopy. The spectra of the as-prepared sample clearly show a typical superparamagnetic behaviour of magnetic clusters with diverging sizes. On the other hand, the reheated sample exhibits a sharp magnetic transition at 16 K. External-field Mössbauer measurements of the latter reveal spin canting to be exclusively present on the octahedral sites which disappears at the magnetic transition temperature. These results show that this spinel compound exhibits a transition to a spin-glass for which the random freezing only occurs on the octahedral sites. 相似文献
75.
A novel mixed‐tribridged dimolybdenum(I) compound [Bn4N][Mo2(μ‐SPh)2(μ‐Cl)(CO)6] (1) has been synthesized from the reaction of Mo2(CO)3(SPh)2 with BU4NCl. Compound 1 was characterized by IR, UV‐Vis and 1H, 13C, 95Mo NMR spectroscopic analyses. The electrochemical behavior was measured by cyclic voltammetry, indicating a quasi‐reversible two‐electron transfer in one step. The crystal structure determined by X‐ray crystallography shows that 1 contains a [Mo2(μ‐S)2(μ‐Cl)]? core with a planar Mo2S2unit and a Cl bridge. The Mo? Mo distance is 0.28709(7) nm, and the Mo‐Cl‐Mo angle is 66.44(4)°. A newface‐sharing bioctahedral structure is discussed. 相似文献
76.
Photoreduction of nitro compounds is accompanied by formation of various radical products that can react with the starting
nitro compound, thus causing deviation of the decomposition kinetics from the first-order kinetics with respect to the nitro
compound. The results of quantum chemical modeling of the reactions of nitro compounds with radicals and the pathways of further
transformations of radical adducts formed in the reactions are presented.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 202–206, February, 2006. 相似文献
77.
The interaction of diethyl (pyridyn-2-ylmethyl)phosphonate (2-pmpe) with Cu(NO3)2 · 6H2O leads to a partial hydrolysis of the starting ligand and formation of the compound of the formula Cu2(2-mpmpe)2(H2O)2(NO3)2, where 2-mpmpe = monoethyl (pyridyn-2-ylmethyl)phosphonate. The crystal and molecular structure of a copper(II) compound was determined by single X-ray diffraction method. Its structure consists of five-coordinated in distorted square planar geometry (CuNO4 chromophore) copper(II) ions doubly bridged by OPO from phosphonate. The Cu?Cu distance is 4.69 Å. The crystal packing is determined by the interdinuclear hydrogen bond system, which leads to a three-dimensional (3D) H-bonds network. The compound was characterized by infrared, ligand field, EPR spectroscopy, and magnetic studies. The magnetic properties of the title compound investigated over the 1.8–300 K, revealed the occurrence of a weak ferromagnetic coupling through phosphonate bridge (J = 1.86 cm−1) and interdimer superexchange coupling through H-bond network (zJ′ = −0.17 cm−1). Spectroscopic and magnetic properties are presented in the light of crystal structure. 相似文献
78.
This paper reports the syntheses and characterization of two phosphonate compounds with layered structures, namely, Mn2(2-C5H4NPO3)2(H2O) (1) and Zn(6-Me-2-C5H4NPO3) (2). In compound 1, double chains are found in which the {Mn2O2} dimers are linked by both aqua and O-P-O bridges. These double chains are connected through corner-sharing of {MnO5N} octahedra and {CPO3} tetrahedra, forming an inorganic layer. The pyridyl groups fill the inter-layer spaces. In compound 2, each {ZnO3N} tetrahedron is vertex-shared with three {CPO3} tetrahedra and vice versa, hence forming an inorganic honeycomb layer. The pyridyl groups reside between the layers. Magnetic studies show that weak antiferromagnetic interactions are mediated between the manganese ions in compound 1. Crystal data for 1: monoclinic, space group C2/c, , , , β=107.3(1)°. For 2: orthorhombic, space group Pbca, , , . 相似文献
79.
Raman Maksimenka Markus Margraf Juliane Khler Alexander Heckmann Christoph Lambert Ingo Fischer 《Chemical physics》2008,347(1-3):436-445
In this article we report a femtosecond time-resolved transient absorption study of a neutral organic mixed-valence (MV) compound with the aim to gain insight into its charge-transfer dynamics upon optical excitation. The back-electron transfer was investigated in five different solvents, toluene, dibutyl ether, methyl-tert-butyl ether (MTBE), benzonitrile and n-hexane. In the pump step, the molecule was excited at 760 nm and 850 nm into the intervalence charge-transfer band. The resulting transients can be described by two time constant. We assign one time constant to the rearrangement of solvent molecules in the charge-transfer state and the second time constant to back-electron transfer to the electronic ground state. Back-electron transfer rates range from 1.5 × 1012 s−1 in benzonitrile through 8.3 × 1011 s−1 in MTBE, around 1.6 × 1011 s−1 in dibutylether and toluene and to 3.8 × 109 s−1 in n-hexane. 相似文献
80.
QM/MM modeling of the hydroxylation of the androstenedione substrate catalyzed by cytochrome P450 aromatase (CYP19A1) 下载免费PDF全文
Ignacio Viciano Raquel Castillo Sergio Martí 《Journal of computational chemistry》2015,36(23):1736-1747
CYP19A1 aromatase is a member of the Cytochrome P450 family of hemeproteins, and is the enzyme responsible for the final step of the androgens conversion into the corresponding estrogens, via a three‐step oxidative process. For this reason, the inhibition of this enzyme plays an important role in the treatment of hormone‐dependent breast cancer. The first catalytic subcycle, corresponding to the hydroxilation of androstenedione, has been proposed to occur through a first hydrogen abstraction and a subsequent oxygen rebound step. In present work, we have studied the mechanism of the first catalytic subcycle by means of hybrid quantum mechanics/molecular mechanics methods. The inclusion of the protein flexibility has been achieved by means of Free Energy Perturbation techniques, giving rise to a free energy of activation for the hydrogen abstraction step of 13.5 kcal/mol. The subsequent oxygen rebound step, characterized by a small free energy barrier (1.5 kcal/mol), leads to the hydroxylated products through a highly exergonic reaction. In addition, an analysis of the primary deuterium kinetic isotopic effects, calculated for the hydrogen abstraction step, reveals values (~10) overpassing the semiclassical limit for the C? H, indicating the presence of a substantial tunnel effect. Finally, a decomposition analysis of the interaction energy for the substrate and cofactor in the active site is also discussed. According to our results, the role of the enzymatic environment consists of a transition state stabilization by means of dispersive and polarization effects. © 2015 Wiley Periodicals, Inc. 相似文献