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991.
Peng Lian Wei‐Peng Lai Hua‐Qiang Cai Shaojun Qiu Bo‐Zhou Wang Jian Lv Yong‐Qiang Xue 《International journal of quantum chemistry》2011,111(14):3571-3577
Nitrosyl cation (NO+) generating reaction HONO + H+ → NO+ + H2O has been theoretically investigated by B3LYP and high‐electron‐correlation QCISD methods with 6‐31G (d,p) basis set. The solvent effects on the geometries, reaction path properties, energies, thermodynamic, and kinetic characters in four solvents (benzene, tetrahydrofuran, acetonitrile, and water) have been calculated using self‐consistent reaction field (SCRF) approach with the polarizable continuum model (PCM). The results show that the activation energy barriers and the relative energies of the products are decreased with increase of the polarities of the solvents, and the reaction is favored in polar solvents thermodynamically and kinetically. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011 相似文献
992.
Lukáš Bučinský Stanislav Biskupič Michal Ilčin Vladimír Lukeš Viliam Laurinc 《Journal of computational chemistry》2011,32(2):356-367
The comparison of coupled cluster with single and double excitations and with perturbative correction of triple excitations [CCSD(T)] ground state potential curves of mercury with rare gases (RG): HgHe and HgXe, at several levels of theory is presented. The scalar relativistic (REL) effects and spin‐orbit coupling effects in the ground state potential curves of these weakly bounded dimers are considered. The CCSD(T) ground state potential curves at the level of the Dirac‐Coulomb Hamiltonian (DCH) are compared with CCSD(T) curves at the level of 4‐component spin‐free modified DCH, the scalar 2nd order Douglas‐Kroll‐Hess (DKH2) and the nonrelativistic (NR‐LL) (Lévy‐Leblond) Hamiltonian. In addition, London‐Drude formula and SCF interaction energy curves are employed in the analysis of different contributions of REL effects in dissociation energies of HgRG and Hg2 dimers. Moreover, the large anharmonicity of the HgHe ground state potential curve is highlighted. The computationally less demanding scalar DKH2 Hamiltonian is employed to calculate the HgXe, Hg2, and Xe2 all electron CCSD(T) ground state potential curves in highly augmented quadruple zeta basis sets. These potential curves are used to simulate the shear viscosity of mercury, xenon, and mercury‐xenon (Hg:Xe) mixture. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011 相似文献
993.
1 INTRODUCTION Silicon is an important kind of semiconductormaterial having been used to produce many sorts ofapparatus, digital and linear integrated circuit andLarge Scale Integrated circuit (LSI), and its clustershave drawn many scientists’ atten… 相似文献
994.
995.
Ray L. Withers Thomas Höche Saeid Esmaeilzadeh Brian Sales 《Journal of solid state chemistry》2004,177(10):3316-3323
High-purity Rb2V3O8 has been grown and temperature-dependent electron and single-crystal X-ray diffraction used to carefully investigate its fresnoite-type reciprocal lattice. In contrast to other recently investigated representatives of the fresnoite family of compounds, Rb2V3O8 is not incommensurately modulated with an incommensurate basal plane primary modulation wave vector given by q∼0.3 〈110〉*. A careful low-temperature electron diffraction study has, however, revealed the existence of weak incommensurate satellite reflections characterized by the primitive primary modulation wave vector q1∼0.16c*. The reciprocal space positioning of these incommensurate satellite reflections, the overall (3+1)-d superspace group symmetry, as well as the shapes of the refined displacement ellipsoids determined from single-crystal XRD refinement, are all consistent with their arising from a distinct type of condensed rigid unit modes (RUMs) of distortion of the Rb2V3O8 parent structure. 相似文献
996.
V. Bertin A. Cruz G. Del Angel M. Castro E. Poulain 《International journal of quantum chemistry》2005,102(6):1092-1105
A comparative study of adsorption of H atoms and H2 molecules on Pd3Cu, Cu4, and Pd4 clusters has been performed through density functional calculations, using the hybrid B3LYP exchange‐correlation functional as implemented in the Gaussian98 program. For Pd atoms the relativistic small‐core effective core potential LANL and LANL2DZ basis set was used and for hydrogen a 6‐31G** basis set was used. The main emphasis is set in the reaction behavior of the different clusters with hydrogen atoms and molecules. We find that full geometry optimization does not appreciably change the metal cluster geometry either for certain reaction modes or the H and H2 capture parameters, but increases the number of reactive sites of the metal clusters. Also, we found that there is charge transfer competition between H and Cu atoms, which drastically diminishes H2 adsorption energy, related to the Pd cluster observed value. Edges and threefold sites are the principal hydrogen adsorption sites. Hydrogen has a great mobility over the metal clusters for different minima, especially when Cu is present; many initial pathways end in the same adsorption site. The observed hydrogen adsorption and binding energies are well reproduced by the calculations. Also, the adsorption mechanisms were determined. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
997.
Anil Kumar Barik Sachindranath Paul Ray J. Butcher Susanta Kumar Kar 《Polyhedron》2000,19(28):2651-2655
Cobalt(III) complexes, of two potentially pyrazole-derived bidentate ligands (with one ambidentate donor site), 3,5-dimethyl-1-(N-methyl/ethyl)thiocarbamylpyrazole (HL1 for N-methyl, HL2 for N-ethyl) have been synthesized and characterized by elemental analyses, IR, UV–Vis and 1H NMR spectral studies. The structure of Co(L2)3 has been determined by single-crystal X-ray diffraction studies. The complex (triclinic, space group P
) has a distorted octahedral structure with the ambidentate ligands coordinated to the Co(III) ion as uninegative bidentate chelating agents via the pyrazole ring nitrogen (tertiary) and the thiocarbamyl iminyl nitrogen atoms. The distortion from the regular octahedral geometry is ascribed to the stereochemical limitations imposed by the planar bidentate ligands. 相似文献
998.
Pamidronate is a bisphosphonate that is effective in treating bone disease including osteopenia and osteoporosis in adults. A sensitive and reliable method for the analysis of pamidronate in whole blood and urine is key to the development of this drug for use in children. A previously described method for pamidronate analysis serum and urine did not consistently detect the drug at satisfactory levels in whole blood. The procedure involves co-precipitation of the bisphosphonates with calcium phosphate, pre-column derivitization with fluorescamine, HPLC utilizing a Nucleosil C(18) column, and fluorescence detection with excitation at 395 nm and emission at 480 nm.Changes to the original protocol included the use of a new internal standard (alendronate), the optimization of the concentration of ethylenediaminetetraacetic acid (EDTA) for dissolving the precipitate, and the elimination of the acidification step prior to deproteinization. The optimum EDTA concentration, which had a significant effect on the labeling capability of fluorescamine, was determined to be 20 mm.A good separation between pamidronate and alendronate was achieved using a heated (40 degrees C ) Nucleosil C(18), 10 micro m particle size column. The mobile phase was an aqueous solution of 1 mm Na(2)EDTA-methanol (97:3, v/v) adjusted to pH 6.5 using a fl ow-rate of 1 mL/min. Fluorescence detection was set at 395 nm for excitation and at 480 nm for emission. The limit of quantitation for pamidronate was 0.5 micro g/mL in whole blood and 0.1 micro g/mL in urine. The method was applied to both whole blood and urine samples from pediatric patients. 相似文献
999.
Tarak Nath MandalSomnath Roy Samik GuptaKinsuk Das Rajat SahaGolam Mostafa Ray J. ButcherCai-Ming Liu Susanta Kumar Kar 《Polyhedron》2011,30(9):1571-1578
Reaction of 2 equiv. amount of copper(II) nitrate hexahydrate with 1 equiv. of 5-methyl-1-pyridin-2-yl-1H-pyrazole-3-carboxylic acid (PyPzCA) in presence of triethyl amine base afforded a 1D coordination polymeric compound [Cu2(PyPzCA)2(H2O)3(NO3)]NO3·H2O (1). Whereas, the same reaction when repeated with 1-(4,6-dimethyl-pyrimidin-2-yl)-5-methyl-1H-pyrazole-3-carboxylic acid (PymPzCA) instead of PyPzCA, a mononuclear compound [Cu(PymPzCA)]·2H2O·NEt3 (2) is formed. Both the complexes are crystallographically characterized. In 1, both the copper atoms (Cu1 and Cu2) have distorted square pyramidal geometry with N2O3 chromophore while, in 2, the central copper atom has a distorted trigonal bipyramidal geometry with N4O chromophore. Complex 1, is a 1D coordination polymer where the metal centers being far apart and are involved in a weak ferromagnetic interaction which is quite unexpected. 相似文献
1000.
DNA中的胞嘧啶在化学致变剂作用下会发生脱氨反应,被认为是导致基因损伤的重要原因之一,本文采用毛细管电泳测定胞嘧啶和尿嘧啶,并将此种新方法用于过氧化氢存在下胞嘧啶脱氨反应的动力学研究,结果显示该反应对过氧化氢和胞嘧啶均为一级反应,反应活化能为70.35kJ.mol^-1,明显低于自发脱氨反应,表明过氧化氢可以加速胞嘧啶脱氨反应。 相似文献