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71.
A distributed fast‐acquisition system for synchronized multi‐technique experiments is presented, in which the collection of metadata and the asynchronous merging of large data volumes from multiple detectors are managed as part of the data collection process. This fast continuous scanning scheme, named FLYSCAN, enables measurement of microscopy data on a timescale of milliseconds per pixel. Proof‐of‐principle multi‐technique experiments, namely scanning X‐ray fluorescence spectrometry combined with absorption, differential phase contrast and dark‐field imaging, have been performed on biological and geological samples.  相似文献   
72.
An α-benzyloxyketone forming part of a strained cyclopentane carbon framework when treated with 10 equiv of anhydrous NaOH in absolute ethanol, for 2 h, affords in a 65% yield a new 2-benzyl-2-hydroxyketone, resulting from an unprecedented double benzylic rearrangement. This new rearrangement could be interpreted as an initial benzylic 1,4-shift between the O-enolate alkoxide of the ketone group and the oxygen atom of the benzyloxy ether, followed by a Curtin type benzylic 1,2-shift. Apart from the novelty and the synthetic application of this transformation it is worth noting the complete regio- and stereoselectivity observed. The structures of both substrate and product have been confirmed by X-ray diffraction studies. A tentative mechanism is herein proposed.  相似文献   
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The crystal structure of the spin‐canted antiferromagnet β‐p‐NCC6F4CNSSN. at 12 K (reported in this work) was found to adopt the same orthorhombic space group as that previously determined at 160 K. The change in the magnetic properties of these two crystal structures has been rigorously studied by applying a first‐principles bottom‐up procedure above and below the magnetic transition temperature (36 K). Calculations of the magnetic exchange pathways on the 160 K structure reveal only one significant exchange coupling (J(d1)=?33.8 cm?1), which generates a three‐dimensional diamond‐like magnetic topology within the crystal. The computed magnetic susceptibility, χ(T), which was determined by using this magnetic topology, quantitatively reproduces the experimental features observed above 36 K. Owing to the anisotropic contraction of the crystal lattice, both the geometry of the intermolecular contacts at 12 K and the microscopic JAB radical–radical magnetic interactions change: the J(d1) radical–radical interaction becomes even more antiferromagnetic (?43.2 cm?1) and two additional ferromagnetic interactions appear (+7.6 and +7.3 cm?1). Consequently, the magnetic topologies of the 12 and 160 K structures differ: the 12 K magnetic topology exhibits two ferromagnetic sublattices that are antiferromagnetically coupled. The χ(T) curve, computed below 36 K at the limit of zero magnetic field by using the 12 K magnetic topology, reproduces the shape of the residual magnetic susceptibility (having subtracted the contribution to the magnetization arising from spin canting). The evolution of these two ferromagnetic JAB contributions explains the change in the slope of the residual magnetic susceptibility in the low‐temperature region.  相似文献   
76.
We have investigated the isomeric distribution and rearrangement of complexes of the type [CoXLn]2+,3+ (where X = Cl-, OH-, H2O, and Ln represents a pentadentate 13-, 14-, and 15-membered tetra-aza or diaza-dithia (N4 or N2S2) macrocycle bearing a pendant primary amine). The preparative procedures for chloro complexes produced almost exclusively kinetically preferred cis isomers (where the pendant primary amine is cis to the chloro ligand) that can be separated by careful cation-exchange chromatography. For L13 and L14 the so-called cis-V isomer is isolated as the kinetic product, and for L15 the cis-VI form (an N-based diastereomer) is the preferred, while for the L14(S) complex both cis-V and trans-I forms are obtained. All these complexes rearrange to form stable trans isomers in which the pendent primary amine is trans to the monodentate aqua or hydroxo ligand, depending on pH and the workup procedure. In total 11 different complexes have been studied. From these, two different trans isomers of [CoClL14(S)]2+ have been characterized crystallographically for the first time in addition to a new structure of cis-V-[CoClL14(S)]2+; all were isolated as their chloride perchlorate salts. Two additional isomers have been identified and characterized by NMR as reaction intermediates. The remaining seven forms correspond to the complexes already known, produced in preparative procedures. The kinetic, thermal, and baric activation parameters for all the isomerization reactions have been determined and involve large activation enthalpies and positive volumes of activation. Activation entropies indicate a very important degree of hydrogen bonding in the reactivity of the complexes, confirmed by density functional theory studies on the stability of the different isomeric forms. The isomerization processes are not simple and even some unstable intermediates have been detected and characterized as part of the above-mentioned 11 forms of the complexes. A common reaction mechanism for the isomerization reactions has been proposed for all the complexes derived from the observed kinetic and solution behavior.  相似文献   
77.
The recent development of short‐wavelength optics (X/EUV, synchrotrons) requires improved metrology techniques in terms of accuracy and curvature dynamic range. In this article a stitching Shack–Hartmann head dedicated to be mounted on translation stages for the characterization of X‐ray mirrors is presented. The principle of the instrument is described and experimental results for an X‐ray toroidal mirror are presented. Submicroradian performances can be achieved and systematic comparison with a classical long‐trace profiler is presented. The accuracy and wide dynamic range of the Shack–Hartmann long‐trace‐profiler head allow two‐dimensional characterizations of surface figure and curvature with a submillimeter spatial resolution.  相似文献   
78.
We present a full optimization of the high harmonics wave front owing to the use of a soft X-ray Hartmann sensor. The sensor was calibrated using a high harmonic source with an accuracy of λ/50 root-mean-square (rms) with λ around 30 nm. We observed a high harmonic wave front of λ/7 rms, which is two times the diffraction-limit, astigmatism being the dominant aberration for every condition of generation. By clipping slightly the unfocused high harmonic beam, it is possible to produce a diffraction-limited beam containing approximately 90% of the incident energy.  相似文献   
79.
We present a direct method of studying the focusability of an intense, short-pulse extreme-ultraviolet (XUV) beam obtained by high-harmonic generation. We perform near-field imaging of the focal spot of five high-harmonic orders strongly focused by a broadband toroidal mirror. To visualize the focal spot directly, we image the fluorescence induced by an XUV beam on a cerium-doped YAG crystal on a visible CCD camera. We can thus measure the harmonic spot size on a single image, together with the Strehl ratio, to evaluate the quality of focusing. Such techniques should become instrumental in optimizing the focusing conditions and reaching intensities required for exploring attosecond nonlinear optics in the XUV range.  相似文献   
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