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41.
Myron S. Huzan Manuel Fix Matteo Aramini Peter Bencok J. Frederick W. Mosselmans Shusaku Hayama Franziska A. Breitner Leland B. Gee Charles J. Titus Marie-Anne Arrio Anton Jesche Michael L. Baker 《Chemical science》2020,11(43):11801
Large single-ion magnetic anisotropy is observed in lithium nitride doped with iron. The iron sites are two-coordinate, putting iron doped lithium nitride amongst a growing number of two coordinate transition metal single-ion magnets (SIMs). Uniquely, the relaxation times to magnetisation reversal are over two orders of magnitude longer in iron doped lithium nitride than other 3d-metal SIMs, and comparable with high-performance lanthanide-based SIMs. To understand the origin of these enhanced magnetic properties a detailed characterisation of electronic structure is presented. Access to dopant electronic structure calls for atomic specific techniques, hence a combination of detailed single-crystal X-ray absorption and emission spectroscopies are applied. Together K-edge, L2,3-edge and Kβ X-ray spectroscopies probe local geometry and electronic structure, identifying iron doped lithium nitride to be a prototype, solid-state SIM, clean of stoichiometric vacancies where Fe lattice sites are geometrically equivalent. Extended X-ray absorption fine structure and angular dependent single-crystal X-ray absorption near edge spectroscopy measurements determine FeI dopant ions to be linearly coordinated, occupying a D6h symmetry pocket. The dopant engages in strong 3dπ-bonding, resulting in an exceptionally short Fe–N bond length (1.873(7) Å) and rigorous linearity. It is proposed that this structure protects dopant sites from Renner–Teller vibronic coupling and pseudo Jahn–Teller distortions, enhancing magnetic properties with respect to molecular-based linear complexes. The Fe ligand field is quantified by L2,3-edge XAS from which the energy reduction of 3dz2 due to strong 4s mixing is deduced. Quantification of magnetic anisotropy barriers in low concentration dopant sites is inhibited by many established methods, including far-infrared and neutron scattering. We deduce variable temperature L3-edge XAS can be applied to quantify the J = 7/2 magnetic anisotropy barrier, 34.80 meV (∼280 cm−1), that corresponds with Orbach relaxation via the first excited, MJ = ±5/2 doublet. The results demonstrate that dopant sites within solid-state host lattices could offer a viable alternative to rare-earth bulk magnets and high-performance SIMs, where the host matrix can be tailored to impose high symmetry and control lattice induced relaxation effects.Taking advantage of synchrotron light source methods, we present the geometric and electronic structure of iron doped in lithium nitride. 相似文献
42.
Liu J Pan D Tseng Y Hopfinger AJ 《Journal of chemical information and computer sciences》2003,43(6):2170-2179
A training set of 55 antifungal p450 analogue inhibitors was used to construct receptor-independent four-dimensional quantitative structure-activity relationship (RI 4D-QSAR) models. Ten different alignments were used to build the models, and one alignment yields a significantly better model than the other alignments. Two different methodologies were used to measure the similarity of the best 4D-QSAR models of each alignment. One method compares the residual of fit between pairs of models using the cross-correlation coefficient of their residuals of fit as a similarity measure. The other method compares the spatial distributions of the IPE types (3D-pharmacophores) of pairs of 4D-QSAR models from different alignments. Optimum models from several different alignments have nearly the same correlation coefficients, r(2), and cross-validation correlation coefficients, xv-r(2), yet the 3D-pharmacophores of these models are very different from one another. The highest 3D-pharmacophore similarity correlation coefficient between any pair of 4D-QSAR models from the 10 alignments considered is only 0.216. However, the best 4D-QSAR models of each alignment do contain some proximate common pharmacorphore sites. A test set of 10 compounds was used to validate the predictivity of the best 4D-QSAR models of each alignment. The "best" model from the 10 alignments has the highest predictivity. The inferred active sites mapped out by the 4D-QSAR models suggest that hydrogen bond interactions are not prevalent when this class of P450 analogue inhibitors binds to the receptor active site. This feature of the 4D-QSAR models is in agreement with the crystal structure results that indicate no ligand-receptor hydrogen bonds are formed. 相似文献
43.
Lytchak Alexander Petrunin Anton 《Journal of Optimization Theory and Applications》2022,194(2):636-642
Journal of Optimization Theory and Applications - We show that cyclic products of projections onto convex subsets of Hadamard spaces can behave in a more complicated way than in Hilbert spaces,... 相似文献
44.
We consider the Hopfield model withM(N)=N patterns, whereN is the number of neurons. We show that if is sufficiently small and the temperature sufficiently low, then there exist disjoint Gibbs states for each of the stored patterns, almost surely with respect to the distribution of the random patterns. This solves a provlem left open in previous work. The key new ingredient is a self-averaging result on the free energy functional. This result has considerable additional interest and some consequences are discussed. A similar result for the free energy of the Sherrington-Kirkpatrick model is also given. 相似文献
45.
H. Weisen F. Hofmann M. J. Dutch J. -M. Moret J. B. Lister A. Pochelon R. A. Pitts M. Anton R. Behn S. Bernel F. Bühlmann R. Chavan B. P. Duval D. Fasel A. Favre S. Franke A. Heym Ch. Hollenstein P. Isoz B. Joye X. Llobet B. Marletaz Ph. Marmillod Y. Martin Ch. Nieswand P. J. Paris A. Perez Z. A. Pietrzyk O. Sauter W. Van Toledo G. Tonetti M. Q. Tran F. Troyon D. J. Ward 《Czechoslovak Journal of Physics》1995,45(12):1095-1110
During the first two years of operation, the TCV tokamak has produced a large variety of plasma shapes and magnetic configurations, with 1.0B
tor1.46T,I
p800kA,k2.05, –0.71. A new shape control algorithm, based on a finite element reconstruction of the plasma current in real time, has been implemented. Vertical growth rates up to 1000s–1 have been stabilized using the external coil system. Ohmic H-modes with Troyon factors (
tor
aB/I
p) up to two and densities up to 2.25×1020m–3, corresponding to the Greenwald limit, have been obtained in diverted discharges. Limiter H-modes with line averaged electron densities up to 1.7×1020m–3 have been obtained in elongated D-shaped plasmas with 360 kAI
P600 kA.Presented at 17th Symposium Plasma Physics and Technology, Prague, June 13–16, 1995.This work was partly supported by the Fonds National Suisse de la Recherche Scientifique. 相似文献
46.
We study the Hopfield model of an autoassociative memory on a random graph onN vertices where the probability of two vertices being joined by a link isp(N). Assuming thatp(N) goes to zero more slowly thanO(1/N), we prove the following results: (1) If the number of stored patternsm(N) is small enough such thatm(N)/Np(N) 0, asN, then the free energy of this model converges, upon proper rescaling, to that of the standard Curie-Weiss model, for almost all choices of the random graph and the random patterns. (2) If in additionm(N) < ln N/ln 2, we prove that there exists, forT< 1, a Gibbs measure associated to each original pattern, whereas for higher temperatures the Gibbs measure is unique. The basic technical result in the proofs is a uniform bound on the difference between the Hamiltonian on a random graph and its mean value. 相似文献
47.
Summary The international motions of a single cyclohexane molecule are studied by molecular dynamics calculations. Classical trajectories are calculated by integrating Newton's equation of motion. The potential functions used are essentially the same as in Allinger's MM2 program which is widely applied for calculations on conformational energies of organic molecules.Geometries and relative energies are reported for all stable low energy conformers and some transition states of cyclohexane. Vibrational frequencies of classical oscillations of individual bonds — computed for ethane as reference system — are close to the experimental values.Two trajectories of the molecular dynamics of cyclohexane were simulated. In the first we were able to follow the process of ring inversion: chair twisted forms inverted chair. The reaction path is analysed in detail and compared with static approaches. The second trajectory shows the correlated reorientation of the possible twisted forms alone. This process is known as pseudorotation.Dedicated to Prof. Dr. Karl Schlögl 相似文献
48.
Synthesis and Absolute Configuration of Clemastine and its Isomers. Condensation of 4-chloro-α-methylbenzhydrylalkohol ( 1 ) with 2-(2-chloroethyl)-1-methylpyrrolidine ( 2 ) gave an isomeric mixture of 2-[2-(p-chloro-α-methyl-=-phenylbenzyloxy)ethyl]-1-methylpyrrolidine ( 3 ) and 4-(p-chloro-=-phenylbenzyloxy)-1-methyl-hexahydroazepin ( 4 ). The separation of the four possible optically active isomers of 3 is described and their absolute configuration established by degradation to (R)- and (S)-1-methyl-2-pyrrolidineethanol ( 6 ), respectively, and by an X-ray cristallographic analysis of the quarternary methiodide of the isomer 3-A . Clemastine (3-A) is (+)-(2R)-2-[2-((αR)-(p-chloro-α-methyl-α-phenylbenzyloxy)ethyl)]-1-methylpyrrolidine. 相似文献
49.
In spite of the higher reactivity of styrene with respect to ethene for the alternating copolymerization with carbon monoxide, catalyzed by chiral (dihydrooxazole)(phosphino)palladium complexes, ethene is preferentially (and randomly) enchained in terpolymerization experiments; enantioface selection for styrene is comparably high in both copolymerization and terpolymerization processes. 相似文献
50.
Kolen'ko YV Kovnir KA Gavrilov AI Garshev AV Meskin PE Churagulov BR Bouchard M Colbeau-Justin C Lebedev OI Van Tendeloo G Yoshimura M 《The journal of physical chemistry. B》2005,109(43):20303-20309
Mesoporous nanosized TiO2 and Zn(x)Ti(1-x)O(2-x) solid solution having a Zn content below 10 mol % with a particles size between 13 and 17 nm are prepared by a template-free sol-gel method followed by high-temperature supercritical drying in 2-propanol. The structural, textural, and electronic properties of the obtained nanomaterials are methodically investigated by using XRD, SEM, TEM, ED, HREM, EDX, ICP-OES, N(2) adsorption-desorption, Raman spectroscopy, and diffuse reflectance UV-vis spectroscopy. It is shown that the proposed synthesis technique leads to the formation of a Zn(x)Ti(1-x)O(2-x) solid solution based on the anatase crystal structure rather than a two-phase sample. High-resolution electron microscopy and electron diffraction indicate that the distribution of zinc atoms over the anatase structure does not lead to a considerable deformation of the crystal structure. 相似文献