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31.
    
Gas phase oxidation of acrolein to acrylic acid on hydrothermally prepared Mo/V/W mixed oxides was investigated by isotopic labeling of acrolein. In this context, perdeuterated acrolein was synthesized for the first time and subsequently used for mechanistic studies. A clear kinetic isotopic effect (KIE) is observed referring to the α-hydrogen-abstraction as the rate-determining step in the selective acrolein oxidation. Furthermore, no change in the selectivity patterns is observed due to the perdeuteration, which confirms that the α-hydrogen-abstraction also acts as the rate-limiting step in the total oxidation of acrolein. Based on these KIE studies combined with additional experiments including D2O-SSITKA and temperature-programmed desorption, a detailed reaction mechanism for acrolein oxidation is proposed.  相似文献   
32.
    
Both compressible and incompressible Navier-Stokes solvers can be used and are used to solve incompressible turbulent flow problems. In the compressible case, the Mach number is then considered as a solver parameter that is set to a small value, M ≈0.1, in order to mimic incompressible flows. This strategy is widely used for high-order discontinuous Galerkin (DG) discretizations of the compressible Navier-Stokes equations. The present work raises the question regarding the computational efficiency of compressible DG solvers as compared to an incompressible formulation. Our contributions to the state of the art are twofold: Firstly, we present a high-performance DG solver for the compressible Navier-Stokes equations based on a highly efficient matrix-free implementation that targets modern cache-based multicore architectures with Flop/Byte ratios significantly larger than 1. The performance results presented in this work focus on the node-level performance, and our results suggest that there is great potential for further performance improvements for current state-of-the-art DG implementations of the compressible Navier-Stokes equations. Secondly, this compressible Navier-Stokes solver is put into perspective by comparing it to an incompressible DG solver that uses the same matrix-free implementation. We discuss algorithmic differences between both solution strategies and present an in-depth numerical investigation of the performance. The considered benchmark test cases are the three-dimensional Taylor-Green vortex problem as a representative of transitional flows and the turbulent channel flow problem as a representative of wall-bounded turbulent flows. The results indicate a clear performance advantage of the incompressible formulation over the compressible one.  相似文献   
33.
    
Herein, a molecular ruthenium-phosphine catalyst system for the effective base-free methyl formate production from carbon dioxide is described. In detail, the novel [Ru(N-triphosCy)(tmm)] complex, bearing sterically demanding cyclohexyl groups in the triphos-ligand structure, enabled in combination with the Lewis acid Al(OTf)3 the selective transformation of carbon dioxide to methyl formate with unprecedented activity. From a mechanistic perspective, in the initial step formic acid is formed, undergoing a consecutive Lewis acid promoted esterification with methanol to methyl formate. This selective transformation with carbon dioxide paves the way to versatile processes for important C1 building blocks.  相似文献   
34.
35.
    
Particle damping is a very promising passive damping technique, however, it is still rarely used in technical applications due to its complex dimensioning. An experimental model is developed in order to investigate the energy dissipation of the dampers regardless of the underlying structure. The testbed consists of a particle box with a free‐free boundary condition which is excited by an acceleration controlled shaker. The loss factor and the energy dissipation are obtained via the complex power. The particle damper can be analyzed over a wide frequency and acceleration range. Different particle numbers are used showing the high potential of particle dampers for different excitation ranges.  相似文献   
36.
    
The reduction of TipMCl3 (Tip=2,4,6‐triisopropylphenyl) (M=Si, Ge) with KC8 in the presence of cyclic alkyl(amino) carbene (cAAC) afforded the acyclic silanylidene and germanylidene anions in the form of potassium salt [K(cAAC)MTip]2 (M=Si ( 1 ); Ge ( 2 )). The silanylidene and germanylidene anions are valence‐isoelectronic to the well‐studied phosphinidene and are a new class of acyclic anions of Group 14. Compounds 1 and 2 were isolated and well characterized by NMR and single‐crystal X‐ray structure analysis. Furthermore, the structure and bonding of compounds 1 and 2 was investigated by computational methods.  相似文献   
37.
The dilatation operator measures scaling dimensions of local operator in a conformal field theory. Algebraic methods of constructing the dilatation operator in four-dimensional N=4 gauge theory are reviewed. These led to the discovery of novel integrable spin chain models in the planar limit. Making use of Bethe ansätze a superficial discrepancy in the AdS/CFT correspondence was found, we discuss this issue and give a possible resolution. To cite this article: N. Beisert, C. R. Physique 5 (2004).

Résumé

L'opérateur de dilatation mesure les dimensions d'échelles des opérateurs locaux des théories conformes des champs. Nous passons en revue les méthodes algébriques de construction de l'opérateur de dilatation pour la théorie de jauge N=4 en quatre dimensions. Ceci nous a conduit à découvrir, dans la limite planaire, de nouveaux modèles intégrables de chaînes de spin. En utilisant l'ansätze de Bethe une incompatibilité avec la correspondance AdS/CFT fut découverte, nous discutons ce problème et une résolution possible. Pour citer cet article : N. Beisert, C. R. Physique 5 (2004).  相似文献   
38.
We experimentally demonstrate that a grating outcoupler used for complex beam shaping (spot-array generation) can produce unintentional optical feedback that severely disturbs the integrated in-plane laser that illuminates the coupler. Simulations show that these outcouplers, in contrast to conventional collimating or focusing outcouplers, tend to produce high levels of feedback in spite of the detuning used to suppress feedback. Further, this feedback is focused to high intensity in the laser gain medium. This focused light acts as a seed for the nonlinear self-focusing that causes wave-front distortion and filamentation, which degrades the beam quality.  相似文献   
39.
We consider adiabatic transport of eigenstates of real Hamiltonians around loops in parameter space. It is demonstrated that loops that map to nontrivial loops in the space of eigenbases must encircle degeneracies. Examples from Jahn-Teller theory are presented to illustrate the test. We show furthermore that the proposed test is optimal.  相似文献   
40.
Amyloid precursor protein (APP) is the precursor protein to amyloid β (Aβ), the main constituent of senile plaques in Alzheimer's disease (AD). Endogenous Aβ peptides reflect the APP processing, and greater knowledge of different APP degradation pathways is important to understand the mechanism underlying AD pathology. When one analyzes longer Aβ peptides by low‐energy collision‐induced dissociation tandem mass spectrometry (MS/MS), mainly long b‐fragments are observed, limiting the possibility to determine variations such as amino acid variants or post‐translational modifications (PTMs) within the N‐terminal half of the peptide. However, by using electron capture dissociation (ECD), we obtained a more comprehensive sequence coverage for several APP/Aβ peptide species, thus enabling a deeper characterization of possible variants and PTMs. Abnormal APP/Aβ processing has also been described in the lysosomal storage disease Niemann–Pick type C and the major large animal used for studying this disease is cat. By ECD MS/MS, a substitution of Asp7 → Glu in cat Aβ was identified. Further, sialylated core 1 like O‐glycans at Tyr10, recently discovered in human Aβ (a previously unknown glycosylation type), were identified also in cat cerebrospinal fluid (CSF). It is therefore likely that this unusual type of glycosylation is common for (at least) species belonging to the magnorder Boreoeutheria. We here describe a detailed characterization of endogenous APP/Aβ peptide species in CSF by using an online top‐down MS‐based method. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   
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