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51.
Uniform catalytic site in Sn-beta-zeolite determined using X-ray absorption fine structure 总被引:1,自引:0,他引:1
Bare SR Kelly SD Sinkler W Low JJ Modica FS Valencia S Corma A Nemeth LT 《Journal of the American Chemical Society》2005,127(37):12924-12932
The Sn silicate zeolite, Sn-beta, has been shown to be an efficient, selective heterogeneous catalyst for Baeyer-Villiger oxidations. Using primarily a multishell fit to extended X-ray absorption fine structure (EXAFS) data, we show that the Sn does not randomly insert into the beta-zeolite structure but rather occupies identical, specific, crystallographic sites. These sites are the T5/T6 sites in the six-membered rings. Moreover, the Sn is substituted in pairs on opposite sides of these six-membered rings. We believe that it is the specific, uniform crystallographic location of the Sn in the beta crystal structure that leads to sites with uniform catalytic activity, and consequently to the high chemical selectivity demonstrated for this catalyst. This manifests itself in the almost enzyme-like selectivity of this catalyst in Baeyer-Villiger oxidations. This uniform site distribution of the Sn suggests that there is likely a symbiotic relationship between the structure-directing agent in the zeolite synthesis and the Sn heteroatoms during the framework formation. 相似文献
52.
Marta?EsoEmail author Soumyadip?Ghosh Jayant?Kalagnanam Laszlo?Ladanyi 《Journal of Heuristics》2005,11(2):147-173
Consider a marketplace operated by a buyer who wishes to procure large quantities of several heterogeneous products. Suppliers submit price curves for each of the commodities indicating the price charged as a function of the supplied quantity. The total amount paid to a supplier is the sum of the prices charged for the individual commodities. It is assumed that the submitted supply curves are piecewise linear as they often are in practice. The bid evaluation problem faced by the procurer is to determine how much of each commodity to buy from each of the suppliers so as to minimize the total purchase price. In addition to meeting the demand, the buyer may impose additional business requirements that restrict which contracts suppliers may be awarded. These requirements may result in interdependencies between the commodities which lead to suboptimal results if the commodities are traded in independent auctions rather than simultaneously. Even without the additional business constraints the bid evaluation problem is NP-hard. The main contribution of our study is a flexible column generation based heuristics that provides near-optimal solutions to the procurer’s bid evaluation problem. Our method scales very well due to the Branch-and-Price technology it is built on. We employ sophisticated rounding and local improvement heuristics to obtain quality solutions. We also developed a test data generator that produces realistic problems and allows control over the difficulty level of the problems using parameters. 相似文献
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Alfred Delville Christian Detellier Andr Gerstmans Pierre Laszlo 《Helvetica chimica acta》1981,64(2):547-555
23Na-chemical shifts for the NaClO4 solute depend markedly upon the composition of binary solvent mixtures of THF with amines (pyridine, piperidine, pyrrolidine, aniline, propylamine, and isopropylamine). These changes, analyzed in a novel application of the Hill formalism, show equality of the intrinsic equilibrium constant K for the successive steps, upon displacement of THF from sodium coordination by one of these amines. The results, which are entirely consistent with tetracoordination of the sodium cation by these solvents, also indicate proportionality of the K values to the amine chemical shifts. 相似文献
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Substantial collective flow is observed in collisions between large nuclei at BNL RHIC (Relativistic Heavy Ion Collider) as evidenced by single-particle transverse momentum distributions and by azimuthal correlations among the produced particles. The data are well reproduced by perfect fluid dynamics. A calculation of the dimensionless ratio of shear viscosity eta to entropy density s by Kovtun, Son, and Starinets within anti-de Sitter space/conformal field theory yields eta/s=variant Planck's over 2pi/4pikB, which has been conjectured to be a lower bound for any physical system. Motivated by these results, we show that the transition from hadrons to quarks and gluons has behavior similar to helium, nitrogen, and water at and near their phase transitions in the ratio eta/s. We suggest that experimental measurements can pinpoint the location of this transition or rapid crossover in QCD. 相似文献
58.
Shao Y Molnar LF Jung Y Kussmann J Ochsenfeld C Brown ST Gilbert AT Slipchenko LV Levchenko SV O'Neill DP DiStasio RA Lochan RC Wang T Beran GJ Besley NA Herbert JM Lin CY Van Voorhis T Chien SH Sodt A Steele RP Rassolov VA Maslen PE Korambath PP Adamson RD Austin B Baker J Byrd EF Dachsel H Doerksen RJ Dreuw A Dunietz BD Dutoi AD Furlani TR Gwaltney SR Heyden A Hirata S Hsu CP Kedziora G Khalliulin RZ Klunzinger P Lee AM Lee MS Liang W Lotan I Nair N Peters B Proynov EI Pieniazek PA Rhee YM 《Physical chemistry chemical physics : PCCP》2006,8(27):3172-3191
Advances in theory and algorithms for electronic structure calculations must be incorporated into program packages to enable them to become routinely used by the broader chemical community. This work reviews advances made over the past five years or so that constitute the major improvements contained in a new release of the Q-Chem quantum chemistry package, together with illustrative timings and applications. Specific developments discussed include fast methods for density functional theory calculations, linear scaling evaluation of energies, NMR chemical shifts and electric properties, fast auxiliary basis function methods for correlated energies and gradients, equation-of-motion coupled cluster methods for ground and excited states, geminal wavefunctions, embedding methods and techniques for exploring potential energy surfaces. 相似文献
59.
El Gabaly F Gallego S Muñoz C Szunyogh L Weinberger P Klein C Schmid AK McCarty KF de la Figuera J 《Physical review letters》2006,96(14):147202
By means of spin-polarized low-energy electron microscopy, we show that the magnetic easy axis of one to three atomic-layer thick cobalt films on Ru(0001) changes its orientation twice during deposition: One-monolayer and three-monolayer thick films are magnetized in plane, while two-monolayer films are magnetized out of plane. The Curie temperatures of films thicker than one monolayer are well above room temperature. Fully relativistic calculations based on the screened Korringa-Kohn-Rostoker method demonstrate that only for two-monolayer cobalt films does the interplay between strain, surface, and interface effects lead to perpendicular magnetization. 相似文献
60.
Laszlo Papp Zoltan Major Laszlo Rinyu Istvan Tóth 《Isotopes in environmental and health studies》2013,49(4):494-511
This paper describes the procedure followed for noble gas measurements for litres, millilitres and microlitres of water samples in our laboratory, including sample preparation, mass spectrometric measurement procedure, and the complete calibrations. The preparation line extracts dissolved gases from water samples of volumes of 0.2 μ l to 3 l and it separates them as noble and other chemically active gases. Our compact system handles the following measurements: (i) determination of tritium concentration of environmental water samples by the 3He ingrowth method; (ii) noble gas measurements from surface water and groundwater; and (iii) noble gas measurements from fluid inclusions of solid geological archives (e.g. speleothems). As a result, the tritium measurements have a detection limit of 0.012 TU, and the expectation value (between 1 and 20 TU) is within 0.2 % of the real concentrations with a standard deviation of 2.4 %. The reproducibility of noble gas measurements for water samples of 20–40 ml allows us to determine solubility temperatures by an uncertainty better than 0.5 °C. Moreover, noble gas measurements for tiny water amounts (in the microlitre range) show that the results of the performed calibration measurements for most noble gas isotopes occur with a deviation of less than 2 %. Theoretically, these precisions for noble gas concentrations obtained from measurements of waters samples of a few microlitres allow us to determine noble gas temperatures by an uncertainty of less than 1 °C. Here, we present the first noble gas measurements of tiny amounts of artificial water samples prepared under laboratory conditions. 相似文献