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91.
92.
We present a review of the fundamental topics of Hartree–Fock theory in quantum chemistry. From the molecular Hamiltonian, using and discussing the Born–Oppenheimer approximation, we arrive at the Hartree and Hartree–Fock equations for the electronic problem. Special emphasis is placed on the most relevant mathematical aspects of the theoretical derivation of the final equations, and on the results regarding the existence and uniqueness of their solutions. All Hartree–Fock versions with different spin restrictions are systematically extracted from the general case, thus providing a unifying framework. The discretization of the one-electron orbital space is then reviewed and the Roothaan–Hall formalism introduced. This leads to an exposition of the basic underlying concepts related to the construction and selection of Gaussian basis sets, focusing on algorithmic efficiency issues. Finally, we close the review with a section in which the most relevant modern developments (especially those related to the design of linear-scaling methods) are commented on and linked to the issues discussed. The paper is intentionally introductory and rather self-contained, and may be useful for non-experts intending to use quantum chemical methods in interdisciplinary applications. Moreover, much material that can be found scattered in the literature has been put together to facilitate comprehension and to serve as a handy reference. 相似文献
93.
José Maria Esbrí Anna Bernaus Marta ávila David Kocman Eva M. García‐Noguero Beatriz Guerrero Xavier Gaona Rodrigo álvarez Gustavo Perez‐Gonzalez Manuel Valiente Pablo Higueras Milena Horvat Jorge Loredo 《Journal of synchrotron radiation》2010,17(2):179-186
The mobility, bioavailability and toxicity of mercury in the environment strongly depend on the chemical species in which it is present in soil, sediments, water or air. In mining districts, differences in mobility and bioavailability of mercury mainly arise from the different type of mineralization and ore processing. In this work, synchrotron‐based X‐ray absorption near‐edge spectroscopy (XANES) has been taken advantage of to study the speciation of mercury in geological samples from three of the largest European mercury mining districts: Almadén (Spain), Idria (Slovenia) and Asturias (Spain). XANES has been complemented with a single extraction protocol for the determination of Hg mobility. Ore, calcines, dump material, soil, sediment and suspended particles from the three sites have been considered in the study. In the three sites, rather insoluble sulfide compounds (cinnabar and metacinnabar) were found to predominate. Minor amounts of more soluble mercury compounds (chlorides and sulfates) were also identified in some samples. Single extraction procedures have put forward a strong dependence of the mobility with the concentration of chlorides and sulfates. Differences in efficiency of roasting furnaces from the three sites have been found. 相似文献
94.
José Ernesto Falcón Dieguez Pablo Rodi Manuel A. Lores Guevara Ana Maria Gennaro 《Applied magnetic resonance》2010,38(4):443-453
An enhanced hemoglobin–membrane association has been previously documented in sickle cell anemia. However, it is not known
how this interaction is modified during the hemoglobin S polymerization process. In this work, we use a model of reconstituted
erythrocytes from ghost membranes whose cytoskeleton proteins had been previously labeled with the 4-maleimido Tempo spin
label, and that were subsequently resealed with hemoglobin S or A solutions. Using electron paramagnetic resonance spectroscopy,
we studied the time dependence of the spectral W/S parameter, indicative of the conformational state of cytoskeleton proteins
(mainly spectrin) under spontaneous deoxygenation, with the aim of detecting the eventual effects due to hemoglobin S polymerization.
The differences observed in the temporal behavior of W/S in erythrocytes reconstituted with both hemoglobins were considered
as experimental evidence of an increment in hemoglobin S–membrane interaction as a result of the polymerization process of
hemoglobin S under spontaneous deoxygenation. 相似文献
95.
5,7-二羟基黄酮与牛血清白蛋白相互作用的研究 总被引:1,自引:0,他引:1
用荧光光谱(FS)和紫外光谱(UV)法研究了5,7-二羟基黄酮与牛血清白蛋白之间的相互作用.实验结果表明,5,7-二羟基黄酮与BSA形成基态复合物导致内源荧光淬灭,淬灭机理主要为静态淬灭.该反应的结合常数4.16×107 L/mol,结合位点数n=1.5;并用同步荧光技术考察了5,7-二羟基黄酮对BSA构象的影响. 相似文献
96.
基于LiF∶F2晶体在近红外飞秒脉冲激光作用下产生F2色心向F3 色心的转变,以及两种色心荧光光谱的不同,实现了荧光反射共焦读出和多光子写入的三维光数据存储的原理性实验.钛宝石再生放大器输出的脉冲宽度100fs、中心波长800nm、重复频率1kHz的超短脉冲激光束,用数值孔径0.68的显微物镜聚焦到LiF:F2晶体内部,通过移动晶体实现了三维逐位式数据写入;用405nm的连续蓝光激发存储位,通过探测F3 色心产生的540nm荧光,实现了对信息位进行快速非破坏性的反射共焦读出.与多光子三维存储的透射共焦散射读出和相衬读出相比,格式与现存光盘技术兼容,结构简单;更重要的是,存储信息位是依靠荧光光谱的变化,折射率变化很小,可以有效增加读出层数. 相似文献
97.
The validity of the paraxial approximation for laser beams in free space is studied via an integral criterion based on the propagation invariants of Helmholtz and paraxial wave equations. This approach allows one to determine the paraxial limit for beams with nondefined spot size and for beams described by more parameters in addition to typical longitudinal wavelength and transverse waist. As examples, the paraxiality of higher-order Hermite, Laguerre, and Bessel-Gaussian beams was completely determined. This method could be extended to nonlinear optics and Bose condensates. 相似文献
98.
Arrays of transparent dielectric nanorods are shown to produce very large local field enhancements at specific resonant conditions. These structures would lead to enhancement of molecular fluorescence signals without quenching. The resonant angular width and field enhancements are analytically derived as a function of wavelength, grating period, rod radius, and dielectric constant. 相似文献
99.
In the field of Brillouin lidar, it has very important significance to find one method that can amplify the Brillouin scattering signal in real time. One new-type Brillouin lidar detection system based on Nd:YAG pulsed laser and polarization control device is designed in this paper. The key point of this detection system is to have two pulsed coherent lights with same frequency, same polarization and same initial phase, of which one beam is taken as the detection wave for generating stimulated Brillouin scattering signal and the other beam is taken as pumping wave for real time and effective amplification of stimulated Brillouin scattering signal. This detection system mainly includes two pulsed lasers and one electro-optical polarization controller. The laser is mainly used to obtain the pulsed lights with same frequency and same phase, and the polarization controller is mainly used to change the polarization state of two coaxial beams to make them change into same polarization state from orthogonal polarization state thus to enable the pumping wave to amplify the backward stimulated Brillouin scattering signal. It is shown from the experimental results that the adoption of this new system can realize the effect of pumping amplification and can increase the signal to noise ratio to a certain extent. 相似文献
100.
Pablo Albella Jose María Saiz Fernando Moreno 《Journal of Quantitative Spectroscopy & Radiative Transfer》2011,112(13):2046-2058
Light scattering from objects in the proximity of surfaces is of fundamental importance in a variety of surface- and field-enhanced optical sensing, spectroscopy and microscopy applications. Here, we present surface monitoring techniques based on the spectral analysis of the scattered light by metal nanoparticles which act as sensors (nanosensors) of sample substrates interacting with them. We will focus on the detection of surface inhomogeneities by studying the modifications undergone by the local fields produced in the surrounding of the nanosensor, giving rise to spectral changes in its Plasmon Resonances. We will also describe an alternative technique where the sample information is obtained from the changes induced in the linear polarization degree of the far field scattered by the tip and due to the interaction with the sample. 相似文献