全文获取类型
收费全文 | 1484篇 |
免费 | 76篇 |
国内免费 | 11篇 |
专业分类
化学 | 1054篇 |
晶体学 | 6篇 |
力学 | 49篇 |
数学 | 266篇 |
物理学 | 196篇 |
出版年
2023年 | 14篇 |
2022年 | 20篇 |
2021年 | 27篇 |
2020年 | 21篇 |
2019年 | 31篇 |
2018年 | 22篇 |
2017年 | 16篇 |
2016年 | 39篇 |
2015年 | 54篇 |
2014年 | 60篇 |
2013年 | 70篇 |
2012年 | 94篇 |
2011年 | 119篇 |
2010年 | 56篇 |
2009年 | 57篇 |
2008年 | 95篇 |
2007年 | 98篇 |
2006年 | 99篇 |
2005年 | 73篇 |
2004年 | 78篇 |
2003年 | 68篇 |
2002年 | 59篇 |
2001年 | 16篇 |
2000年 | 22篇 |
1999年 | 24篇 |
1998年 | 13篇 |
1997年 | 15篇 |
1996年 | 18篇 |
1995年 | 13篇 |
1994年 | 15篇 |
1993年 | 7篇 |
1992年 | 10篇 |
1991年 | 10篇 |
1990年 | 13篇 |
1989年 | 4篇 |
1988年 | 6篇 |
1987年 | 7篇 |
1986年 | 8篇 |
1985年 | 8篇 |
1984年 | 7篇 |
1983年 | 6篇 |
1982年 | 12篇 |
1981年 | 10篇 |
1980年 | 10篇 |
1979年 | 9篇 |
1978年 | 9篇 |
1977年 | 5篇 |
1976年 | 5篇 |
1975年 | 4篇 |
1974年 | 7篇 |
排序方式: 共有1571条查询结果,搜索用时 31 毫秒
141.
Density Functional Theory and post‐Hartree Fock calculations reveal an unusual energy profile for Zn? S and Zn? N bond dissociation reactions in several [Zn(SR)4]2? and [Zn(Im)(SR)3]? complexes. The Zn? S bond dissociation in tetrathiolate dianions, which is highly exothermic in the gas phase, proceeds through a late transition state which can be rationalized on the basis of an avoided crossing resulting from Coulomb repulsion between the anionic fragments and ligand‐to‐metal charge‐transfer in the [Zn(SR)4]2? complexes. When solvation models for water, DMSO, or acetonitrile are included, some complexes become stable while others are metastable, so this constitutes the first theoretical model which is in full agreement with the experimental data for various [Zn(SR)4]2?, [Zn(SR)3]?, and [Zn(Im)(SR)3]? complexes. The analysis given here indicates that the Zn(Cys)4 and Zn(His)(Cys)3 cores of numerous proteins are metastable with respect to Zn? S and Zn? N bond dissociation, respectively. This is consistent with the kinetic lability at the zinc‐centers and illustrates that in nature, thermodynamic stability is imparted upon the zinc cores by the protein environment. 相似文献
142.
Krzysztof Ejsmont Joel Boeglin Claude Didierjean Gilles Guichard Christian Jelsch 《Acta Crystallographica. Section C, Structural Chemistry》2010,66(6):o292-o294
The crystal structure of the title compound, C16H23N3O4·CH3CN, was refined using a multipolar atom model transferred from an experimental electron‐density database. The refinement showed some improvement in crystallographic statistical indices compared with the independent atom model. The triazepane ring adopts a twist‐boat conformation. In the crystal structure, the molecule forms intermolecular contacts with 14 different neighbours. There are two N—H...O and one C—H...O intermolecular hydrogen bond. 相似文献
143.
Gilles Gasser Jonathan D. Carr Stephen J. Green Sean M. Cafferkey James H.R. Tucker 《Journal of organometallic chemistry》2010,695(2):249-3763
Two new ligand derivatives of ferrocene, namely N-4-[3,5-di-(2-pyridyl)-1,2,4-triazoyl]ferrocene carbimine (L1) and N-4-[3,5-di-(2-pyridyl)-1,2,4-triazoyl]ferrocene carbamide (L2), were synthesised in good yields by reacting the known compound 3,5-di-pyridine-2-yl-[1,2,4]triazol-4-ylamine (1) with ferrocenecarbaldehyde and chlorocarbonyl ferrocene, respectively. The structures of L1 and L2 were determined by X-ray crystallography. The complexation of L1 and L2 with CuI, AgI, ZnII and CdII was studied by NMR and UV-vis spectroscopies, as well as by electrochemistry, with titrations used to determine metal:ligand stoichiometries. The cyclic voltammograms of L1 and L2 and their respective complexes indicated reversible one-electron transfers corresponding to the Fc0/+ redox couple (Fc = ferrocene), with formal electrode potentials shifting to more positive values upon metal complexation. 相似文献
144.
Alban A. Letailleur Sergey Yu Grachev Elin Søndergård Christophe Couteau Gilles Lérondel Emmanuelle Peter 《Journal of luminescence》2011,131(12):2646-2651
The application of alumina-doped ZnO (AZO) films as luminescent material for large area lighting sources has been evaluated. Thin films were grown on quartz using magnetron sputtering and subsequently annealed under argon atmosphere in a rapid thermal annealing experiment. Below 550 °C, red-shift of the optical band gap and increase of the visible emission are observed in agreement with Al diffusion and formation of interstitial oxygen atoms. At temperatures higher than 800 °C, diffusion is activated and Ostwald ripening leads to the formation of larger grains and an increase of the crystalline phase. The photoluminescence (PL) intensity is enhanced, specifically in the UV range. As a result the emission spectrum of AZO thin films can be adjusted by the annealing conditions, with equal contributions from the UV and orange parts of the PL spectrum resulting in an efficient white emission as quantified using the color space map of the Commission Internationale de l'Éclairage. 相似文献
145.
We provide a resolution of one of the long-standing puzzles in the theory of disordered systems. By reformulating the functional renormalization group for the critical behavior of the random field Ising model in a superfield formalism, we are able to follow the associated supersymmetry and its spontaneous breaking along the functional renormalization group flow. Breaking is shown to occur below a critical dimension d(DR) ? 5.1 and leads to a breakdown of the "dimensional reduction" property. We compute the critical exponents as a function of dimension and give evidence that scaling is described by three independent exponents. 相似文献
146.
Laroche M Bartolacci C Cadier B Gilles H Girard S Lablonde L Robin T 《Optics letters》2011,36(19):3909-3911
Pulsed blue light at 489 nm has been generated by second-harmonic-generation of a nanosecond pulsed master-oscillator power amplifier system based on a short Yb(3+) doped single-mode fiber amplifier at 978 nm and an external-cavity diode laser as seed source. The Yb(3+)-doped fiber was core-pumped by a W type Nd(3+) doped double-clad fiber laser operating on the transition near 930 nm ((4)F(3/2)→(4)I(9/2)). 520 mW of average power was generated at 489 nm using a periodically poled MgO:LiNbO(3), corresponding to a conversion efficiency of 34%. 相似文献
147.
Vigreux C Barthélémy E Bastard L Broquin JE Barillot M Ménard S Parent G Pradel A 《Optics letters》2011,36(15):2922-2924
The feasibility of all-telluride integrated optics devices based on waveguides presenting a single-mode behavior in the spectral range (10-20 μm) is demonstrated. These waveguides are constituted of a several micrometer thick Te(82)Ge(18) film deposited onto a Te(75)Ge(15)Ga(10) bulk glass substrate by thermal coevaporation and further etched by reactive ion etching under the CHF(3)/O(2)/Ar atmosphere. The obtained structures were proven to behave as channel waveguides with a good single-mode transmission over the whole spectral range. These results allowed validating our technological solution for the fabrication of integrated optics modal filters for spatial interferometry. 相似文献
148.
A polemic arose recently about the applicability of the t-expansion method to the calculation of the ground state energy E0 of the Rabi model. For specific choices of the trial function and very large number of involved connected moments, the t-expansion results are rather poor and exhibit considerable oscillations. In this Letter, we formulate the t-expansion method for trial functions containing two free parameters which capture two exactly solvable limits of the Rabi Hamiltonian. At each order of the t-series, E0 is assumed to be stationary with respect to the free parameters. A high accuracy of E0 estimates is achieved for small numbers (5 or 6) of involved connected moments, the relative error being smaller than 10−4 (0.01%) within the whole parameter space of the Rabi Hamiltonian. A special symmetrization of the trial function enables us to calculate also the first excited energy E1, with the relative error smaller than 10−2 (1%). 相似文献
149.
Julien Alexandre Dit Sandretto Gilles Trombettoni David Daney 《Mathematics in Computer Science》2014,8(3-4):479-493
An actual model in simulation (e.g. in chemistry) or control (e.g. in robotics) is often too complex to use, and sometimes impossible to obtain. To handle a system in practice, a simplification of the real model is often necessary. This simplification goes through some hypotheses made on the system or the modeling approach. These hypotheses are rarely verified whereas they could lead to an inadmissible model, over approximated for its use. In this paper, we propose a method that qualifies the simplification validity for all models that can be expressed by real-valued variables involved in closed-form relations and depending on parameters. We based our approach on a verification of a quality threshold on the hypothesis relevance. This method, based on interval analysis, checks the acceptance of the hypothesis in a full range of the whole model space, and gives bounds on the quality threshold and on the model parameters. Our approach is experimentally validated on a robotic application. 相似文献
150.
Xiang-Yang Zhang Gilles Févotte Liang Zhong Gang Qian Xing-Gui Zhou Wei-Kang Yuan 《Journal of Crystal Growth》2010,312(19):2747-2755
The influence of malic acid, which acts as an impurity on the cooling crystallization of zinc lactate is investigated in this paper by monitoring the relative supersaturation and the number of crystals during crystallization. The presence of malic acid increases the solution solubility and makes the metastable zone wider; it also changes the habit of the crystal. The purity of the final products is shown to be influenced by the amount and size of seed crystals, cooling rate, seeding temperature and final temperature, but appears to depend mainly on the particle size and level of supersaturation. Residual supersaturation thresholds are observed that depend on the final temperature. A model is proposed to predict the steady-state supersaturation value from the final temperature at a given impurity concentration. This model is based on Kubota and Gibbs equations. 相似文献