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11.
Brinkmann C Faske S Vogel M Nilges T Heuer A Eckert H 《Physical chemistry chemical physics : PCCP》2006,8(3):369-378
The relation between structure and ion dynamics in the three polymorphs of Ag(5)Te(2)Cl has been investigated using (109)Ag, (125)Te, and (35)Cl NMR spectroscopies. Specifically, the influence of the structural phase transitions observed near 240 K (P2(1)/c<-->P2(1)/n) and near 332 K (P2(1)/n<-->I4/mcm) upon silver ion mobilities has been studied by temperature dependent (109)Ag NMR lineshapes and spin-lattice relaxation times. While the superionic high temperature phase alpha-Ag(5)Te(2)Cl is characterized by a molten cationic sublattice, fast ion dynamics in the medium-temperature phase beta-Ag(5)Te(2)Cl occurs in spatially restricted regions comprising all the crystallographically distinct silver sites. Temperature dependent magic-angle-spinning linewidths yield an activation energy of 0.38 eV, consistent with 0.44 eV measured from dc electric conductivities. For the low-temperature gamma-modification, results of two- and three-time (109)Ag correlation spectroscopies provide a detailed insight into the nature of the silver ionic hopping motion. Temperature dependent jump rates measured by two-time correlation functions yield an activation energy E(a)= 0.48 eV. (109)Ag NMR three-time correlation functions indicate that the non-exponential relaxation behavior of the silver ions can be attributed to a broad distribution of jump rates rather than correlated forward-backward jumps. Nevertheless, all the silver ions are mobile down to temperatures of about 185 K. 相似文献
12.
A purification process was developed for the separation of a semi-synthetic ascomycin derivative from its by-products. The process consists of a silica gel filtration and crystallization step prior to two simulated moving bed (SMB) separations, where in the first part the polar by-products and in the second part the apolar by-products were removed. The desired purity was achieved in a final crystallization step. Key elements of the whole process were the design of the first crystallization to obtain a product feasible for SMB chromatography and the specification of operating parameters for the two corresponding SMB steps. Starting from a crude product with an assay of only 44.9% an overall yield for the whole process of 81.0% was achieved with a final purity of >98%. 相似文献
13.
The electrophoretic mobility of three-arm asymmetric star DNA molecules, produced by incorporating a short DNA branch at the midpoint of rigid-rod linear DNA fragments, is investigated in polyacrylamide gels. We determine how long the added branch must be to separate asymmetric star DNA from linear DNA with the same total molecular weight. This work focuses on two different geometric progressions of small DNA molecules. First, branches of increasing length were introduced at the center of a linear DNA fragment of constant length. At a given gel concentration, we find that relatively small branch lengths are enough to cause a detectable reduction in electrophoretic mobility. The second geometric progression starts with a small branch on a linear DNA fragment. As the length of this branch is increased, the DNA backbone length is decreased such that the total molar mass of the molecule remains constant. The branch length was then increased until the asymmetric branched molecule becomes a symmetric three-arm star polymer, allowing the effect of molecular topology on mobility to be studied independent of size effects. DNA molecules with very short branches have a mobility smaller than linear DNA of identical molar mass. The reason for this change in mobility when branching is introduced is not known, however, we explore two possible explanations in this article. (i) The branched DNA could have a greater interaction with the gel than linear DNA, causing it to move slower; (ii) the linear DNA could have modes of motion or access to pores that are unavailable to the branched DNA. 相似文献
14.
Molecule deposition on a prepatterned substrate is a recently developed technique to generate desired structures of organic molecules on surfaces via self-organization. For the case of prepatterned stripes, the time-resolved process of structure formation is studied via lattice Monte Carlo simulations. By systematic variation of the interaction strength, three distinct growth regimes can be identified: localized growth, bulge formation, and cluster formation. All three growth regimes can be recovered in the experiment when choosing appropriate organic molecules. Some key microscopic observables, reflecting the properties of the structure formation, display a non-monotonous dependence on the interaction strength. 相似文献
15.
A close coupling between the structure and size of hematite flocs formed in suspension and the permeability of the cake that accumulates on ultrafiltration membranes is observed. Specific resistances of cakes formed from flocs generated under diffusion-limited aggregation conditions are at least an order of magnitude lower than those of cakes formed from flocs generated under reaction-limited aggregation conditions. Similar effects are observed whether the aggregation regime is controlled by salt concentration, pH, or added organic anions. This dramatic difference in cake resistance is considered to arise from the size and fractal properties of the hematite assemblages. The ease of fluid flow through these assemblages will be influenced both by the fractal dimension of the aggregates and by their size relative to primary particle size (since, for fractal aggregates, porosity increases as the size of the aggregate increases). The size and strength of aggregates are also important determinants of the relative effects of permeation drag, shear-induced diffusion, and inertial lift and result, in the studies reported here, in relatively similar rates of particle deposition for both rapidly and slowly formed aggregates. The results presented here suggest that control of cake permeability (and mass) via control of aggregate size and structure is an area with scope for further development though the nature and extent of compaction effects in modifying the fractal properties of aggregates generated in suspension requires attention. Copyright 1999 Academic Press. 相似文献
16.
This paper establishes a foundation of non-conforming boundary elements. We present a discrete weak formulation of hypersingular
integral operator equations that uses Crouzeix–Raviart elements for the approximation. The cases of closed and open polyhedral
surfaces are dealt with. We prove that, for shape regular elements, this non-conforming boundary element method converges
and that the usual convergence rates of conforming elements are achieved. Key ingredient of the analysis is a discrete Poincaré–Friedrichs
inequality in fractional order Sobolev spaces. A numerical experiment confirms the predicted convergence of Crouzeix–Raviart
boundary elements.
Norbert Heuer is supported by Fondecyt-Chile under grant no. 1080044. F.-J. Sayas is partially supported by MEC-FEDER Project
MTM2007-63204 and Gobierno de Aragón (Grupo Consolidado PDIE). 相似文献
17.
In this paper we characterise the graphs containing a \(\mathbb {Z} \times \mathbb {Z}\) grid minor in a similar way as it has been done by Halin for graphs with an \(\mathbb {N} \times \mathbb {Z}\) grid minor. Using our characterisation, we describe the structure of graphs without \(\mathbb {Z} \times \mathbb {Z}\) grid minors in terms of tree-decompositions. 相似文献
18.
Geometriae Dedicata - We show that every plumbing of disc bundles over surfaces whose genera satisfy a simple inequality may be embedded as a convex submanifold in some closed hyperbolic... 相似文献
19.
We investigate the minimum residual method for symmetric, indefinite linear systems of a so‐called dual–dual structure. These systems arise when using a combined dual‐mixed finite element method with a Dirichlet‐to‐Neumann mapping to solve a class of exterior transmission problems. As a model problem we consider an elliptic equation of divergence form coupled with the Laplace equation in an unbounded region of the plane. We give abstract convergence results for the preconditioned minimum residual method for the solution of linear systems of the special dual–dual structure. For our model problem, we show that this iterative method provides an efficient solution procedure where standard preconditioners can directly be used. Copyright © 2001 John Wiley & Sons, Ltd. 相似文献
20.
We present and analyze a preconditioner of the additive Schwarz type for the mortar boundary element method. As a basic splitting, on each subdomain we separate the degrees of freedom related to its boundary from the inner degrees of freedom. The corresponding wirebasket-type space decomposition is stable up to logarithmic terms. For the blocks that correspond to the inner degrees of freedom standard preconditioners for the hypersingular integral operator on open boundaries can be used. For the boundary and interface parts as well as the Lagrangian multiplier space, simple diagonal preconditioners are optimal. Our technique applies to quasi-uniform and non-uniform meshes of shape-regular elements. Numerical experiments on triangular and quadrilateral meshes confirm theoretical bounds for condition and MINRES iteration numbers. 相似文献