全文获取类型
收费全文 | 12881篇 |
免费 | 2004篇 |
国内免费 | 2201篇 |
专业分类
化学 | 10491篇 |
晶体学 | 183篇 |
力学 | 692篇 |
综合类 | 155篇 |
数学 | 1496篇 |
物理学 | 4069篇 |
出版年
2024年 | 21篇 |
2023年 | 141篇 |
2022年 | 370篇 |
2021年 | 347篇 |
2020年 | 394篇 |
2019年 | 479篇 |
2018年 | 398篇 |
2017年 | 432篇 |
2016年 | 565篇 |
2015年 | 651篇 |
2014年 | 783篇 |
2013年 | 979篇 |
2012年 | 1129篇 |
2011年 | 1186篇 |
2010年 | 874篇 |
2009年 | 890篇 |
2008年 | 995篇 |
2007年 | 868篇 |
2006年 | 759篇 |
2005年 | 712篇 |
2004年 | 617篇 |
2003年 | 458篇 |
2002年 | 513篇 |
2001年 | 430篇 |
2000年 | 331篇 |
1999年 | 252篇 |
1998年 | 218篇 |
1997年 | 176篇 |
1996年 | 147篇 |
1995年 | 125篇 |
1994年 | 133篇 |
1993年 | 103篇 |
1992年 | 98篇 |
1991年 | 84篇 |
1990年 | 90篇 |
1989年 | 60篇 |
1988年 | 59篇 |
1987年 | 47篇 |
1986年 | 41篇 |
1985年 | 27篇 |
1984年 | 14篇 |
1983年 | 18篇 |
1982年 | 16篇 |
1981年 | 8篇 |
1980年 | 9篇 |
1979年 | 6篇 |
1977年 | 6篇 |
1975年 | 3篇 |
1957年 | 4篇 |
1936年 | 8篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
951.
Jin H Yang H Yu M Liu Z Beavers CM Olmstead MM Balch AL 《Journal of the American Chemical Society》2012,134(26):10933-10941
Two isomers of Sm@C(92) and four isomers of Sm@C(94) were isolated from carbon soot obtained by electric arc vaporization of carbon rods doped with Sm(2)O(3). Analysis of the structures by single-crystal X-ray diffraction on cocrystals formed with Ni(II)(octaethylporphyrin) reveals the identities of two of the Sm@C(92) isomers: Sm@C(92)(I), which is the more abundant isomer, is Sm@C(1)(42)-C(92), and Sm@C(92)(II) is Sm@C(s)(24)-C(92). The structure of the most abundant form of the four isomers of Sm@C(94), Sm@C(94)(I), is Sm@C(3v)(134)-C(94), which utilizes the same cage isomer as the previously known Ca@C(3v)(134)-C(94) and Tm@C(3v)(134)-C(94). All of the structurally characterized isomers obey the isolated pentagon rule. While the four Sm@C(90) and five isomers of Sm@C(84) belong to common isomerization maps that allow these isomers to be interconverted through Stone-Wales transformations, Sm@C(1)(42)-C(92) and Sm@C(s)(24)-C(92) are not related to each other by any set of Stone-Wales transformations. UV-vis-NIR spectroscopy and computational studies indicate that Sm@C(1)(42)-C(92) is more stable than Sm@C(s)(24)-C(92) but possesses a smaller HOMO-LUMO gap. While the electronic structures of these endohedrals can be formally described as Sm(2+)@C(2n)(2-), the net charge transferred to the cage is less than two due to some back-donation of electrons from π orbitals of the cage to the metal ion. 相似文献
952.
Metal/semiconductor hybrid materials of various sizes and morphologies have many applications in areas such as catalysis and sensing. Various organic agents are necessary to stabilize metal nanoparticles during synthesis, which leads to a layer of organic compounds present at the interfaces between the metal particles and the semiconductor supports. Generally, high-temperature oxidative treatment is used to remove the organics, which can extensively change the size and morphology of the particles, in turn altering their activity. Here we report a facile method for direct growth of noble-metal particles on WO(3) through an in situ redox reaction between weakly reductive WO(2.72) and oxidative metal salts in aqueous solution. This synthetic strategy has the advantages that it takes place in one step and requires no foreign reducing agents, stabilizing agents, or pretreatment of the precursors, making it a practical method for the controlled synthesis of metal/semiconductor hybrid nanomaterials. This synthetic method may open up a new way to develop metal-nanoparticle-loaded semiconductor composites. 相似文献
953.
Shao Z Li H Zhang S Li J Dai Z Mo Y Bae YJ Kim MS 《The Journal of chemical physics》2012,136(6):064308
The energy levels of CH(3)Cl(+)X?(2)E showing strong spin-vibronic coupling effect (Jahn-Teller effect) have been measured up to 3500 cm(-1) above the ground vibrational state using one-photon zero-kinetic energy photoelectron and mass-analyzed threshold ionization spectroscopic method. Theoretical calculations have been also performed to calculate the spin-vibronic energy levels using a diabatic model and ab initio adiabatic potential energy surfaces (PESs). In the theoretical calculations the diabatic potential energy surfaces are expanded by the Taylor expansions up to the fourth-order including the multimode vibronic interactions. The calculated spin-orbit energy splitting (224.6 cm(-1)) for the ground vibrational state is in good agreement with the experimental data (219 ± 3 cm(-1)), which indicates that the Jahn-Teller and the spin-orbit coupling have been properly described in the theoretical model near the zero-point energy level. Based on the assignments predicted by the theoretical calculations, the experimentally measured energy levels were fitted to those from the diabatic model by optimizing the main spectroscopic parameters. The PESs from the ab initio calculations at the level of CASPT2/vq(t)z were thus compared with those calculated from the experimentally determined spectroscopic parameters. The theoretical diagonal elements in the diabatic potential matrix are in good agreement with those determined using the experimental data, however, the theoretical off-diagonal elements appreciably deviate from those determined using the experimental data for geometric points far away from the conical intersections. It is also concluded that the JT effect in CH(3)Cl(+) mainly arises from the linear coupling and the mode coupling between the CH(3) deform (υ(5)) and CH(3) rock (υ(6)) vibrations. The mode couplings between the symmetric C-Cl stretching vibration υ(3) with υ(5) and υ(6) are also important to understand the spin-vibronic structure of the molecule. 相似文献
954.
Geometries and dissociation energies of water molecules on Al(n) (n = 2-25) clusters were investigated using density functional theory with all electron relativistic spin-polarized calculations under the generalized gradient approximation. An extensive structure search was performed to identify the low-energy conformations of Al(n)H(2)O complexes for each size. Optimal adsorption sites were assigned for low-energy isomers of the clusters. Size and site specific dependences were studied for the Al(n)H(2)O complexes in stabilities, geometries, adsorption energies, dissociation energies, Al-O bond lengths, and other characteristic quantities. The stabilities and geometries revealed that H atom in H(2)O is not inclined to bond with Al atoms. The most stable Al(n)H(2)O configurations for each size tend to correspond to the most stable bare Al(n) cluster except of Al(6) and Al(24) clusters. The HO bond lengths increase generally 0.01 ? with respect to the isolated H(2)O in all of the adsorption complexes. The dissociation energy of an isolated H(2)O into HO and H was 5.39 eV, which decreased about two-thirds to the energy range of 0.83-2.12 eV with the help of Al(n) clusters. In spite of the fluctuations, the dissociation energies of Al(n)H(2)O complexes rise with the size increasing as a whole. In addition, we also found that the bare Al(n) clusters with high vertical ionization potentials usually have high dissociation energies of H(2)O in the corresponding adsorption models. The energetically preferred spin-multiplicity of all the odd-n Al(n)H(2)O complexes is doublet, and it is singlet for all the even-n complexes with exception of Al(2)H(2)O which is triplet. 相似文献
955.
Salari M Aboutalebi SH Chidembo AT Nevirkovets IP Konstantinov K Liu HK 《Physical chemistry chemical physics : PCCP》2012,14(14):4770-4779
Here, we report the fabrication of self-organized titania (TiO(2)) nanotube array supercapacitor electrodes through controlled phase transformation of TiO(2), with aerial capacitances as high as 2.6 mF cm(-2), which far exceeds the values so far reported in the literature. The role of phase transformation in the electrochemical charge-discharge behaviour of nanocrystalline TiO(2) nanotubes is investigated and discussed in detail. The ease of synthesis and the exceptional electrochemical properties make these nanotube arrays an alternative candidate for use in energy storage devices. 相似文献
956.
957.
Liang‐Hua Zou Dr. Adam Johannes Johansson Dr. Erik Zuidema Prof. Dr. Carsten Bolm 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(25):8144-8152
An efficient catalytic system for Sonogashira–Hagihara‐type reactions displaying ligand acceleration in the copper‐catalyzed formation of C(sp2)? C(sp) bonds is described. The structure of the ligand plays a key role for the coupling efficiency. Various copper sources show excellent catalytic activity, even in sub‐mol % quantities. A wide variety of substituents is tolerated in the substrates. Mechanistic details have been revealed by kinetic measurements and DFT calculations. 相似文献
958.
Der‐Lii M. Tzou Lin‐Kai Ni Mei‐Man Chen Min‐Chuan Chiou Li‐Chou Chen Shan‐Te Hsu Kuo‐Lung Ku Chien‐Chung Cheng 《中国化学会会志》2013,60(9):1107-1112
Solid‐state Nuclear Magnetic Resonance (ss‐NMR) 13C single‐pulse excitation spectroscopy in combination with the magic‐angle spinning (MAS) technique was applied to a series of Phalaenopsis tissues, including the leaf, sheath, stem, and root, at different growth and spiking periods. Compared with{1H}/13C cross‐polarization MAS spectra, the 13C single‐pulse excitation MAS spectra displayed very distinct spectral patterns, recognizable as fingerprints of the tissues studied. 1Here, we demonstrate that solid‐state 13C single‐pulse excitation NMR spectroscopy provides a direct and robust analytical tool for studying the various tissues of Phalaenopsis in different growth and spiking induction periods. 相似文献
959.
In this study, porous TiO2 thin films were prepared by the sol‐gel method employing polyethylene glycol 1000 (PEG 1000) as an organic template. Pore sizes were adjusted by varying the concentration of PEG 1000. The optimal PEG concentration range required to form TiO2 films with a regular porous structure was investigated and was found to be 0.01–0.015 M. As the PEG 1000 concentration increased, the surface of these films became rougher because of larger pores. Degradation of methylene blue (MB) under UV irradiation was used to determine the photocatalytic activity of the films. In addition, the effect of the pH value of the MB solution on the films was evaluated by controlling its pH value at 5, 7, and 9. The results showed that the photocatalytic activity was correlated to the pore size and pore density of the thin films. TiO2 thin films possessing pore sizes in the diameter range of 35–85 nm exhibited the best conversion of 98% after 8 h of UV irradiation when the pH value was 7. 相似文献
960.
Qing Lv Qing Zhang Wentao Li Haiyu Li Pi Li Qiang Ma Xianshuang Meng Meiling Qi Hua Bai 《Journal of separation science》2013,36(21-22):3534-3549
This paper presents a method for the simultaneous determination of 48 fragrance allergens in four types of toys (plastic toys, play clays, plush toys, and paper toys) based on GC with ion trap MS/MS. Compared with single‐stage MS, MS/MS is superior in terms of the qualification and quantification of a large range of compounds in complicated matrices. Procedures for extraction and purification were optimized for each toy type. The method proved to be linear over a wide range of concentrations for all analytes with correlation coefficients between 0.9768 and 0.9999. Validation parameters, namely, LODs and LOQs, ranged from 0.005–5.0 and from 0.02–20 mg/kg, respectively. Average recoveries of target compounds (spiked at three concentration levels) were in the range of 79.5–109.1%. Intraday and interday repeatabilities of the proposed method varied from 0.7–10.5% and from 3.1–13.4%, respectively. The proposed method was used to monitor fragrance allergens in commercial toy products. Our findings indicate that this method is an accurate and effective technique for analyzing fragrance allergens in materials composed of complex components. 相似文献