全文获取类型
收费全文 | 3800篇 |
免费 | 368篇 |
国内免费 | 415篇 |
专业分类
化学 | 2936篇 |
晶体学 | 56篇 |
力学 | 221篇 |
综合类 | 28篇 |
数学 | 333篇 |
物理学 | 1009篇 |
出版年
2024年 | 4篇 |
2023年 | 41篇 |
2022年 | 48篇 |
2021年 | 86篇 |
2020年 | 102篇 |
2019年 | 97篇 |
2018年 | 82篇 |
2017年 | 85篇 |
2016年 | 104篇 |
2015年 | 119篇 |
2014年 | 152篇 |
2013年 | 324篇 |
2012年 | 193篇 |
2011年 | 183篇 |
2010年 | 172篇 |
2009年 | 251篇 |
2008年 | 247篇 |
2007年 | 266篇 |
2006年 | 237篇 |
2005年 | 215篇 |
2004年 | 205篇 |
2003年 | 163篇 |
2002年 | 133篇 |
2001年 | 125篇 |
2000年 | 128篇 |
1999年 | 85篇 |
1998年 | 96篇 |
1997年 | 80篇 |
1996年 | 70篇 |
1995年 | 76篇 |
1994年 | 61篇 |
1993年 | 63篇 |
1992年 | 49篇 |
1991年 | 42篇 |
1990年 | 28篇 |
1989年 | 27篇 |
1988年 | 20篇 |
1987年 | 13篇 |
1986年 | 22篇 |
1985年 | 22篇 |
1984年 | 13篇 |
1983年 | 6篇 |
1982年 | 9篇 |
1981年 | 10篇 |
1980年 | 5篇 |
1979年 | 9篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1973年 | 3篇 |
排序方式: 共有4583条查询结果,搜索用时 15 毫秒
71.
泸定县地处川西高原与四川盆地的过渡地带,地质环境条件复杂,分布泥石流沟127条,发育密度054条·10km-2。在遥感解译和地面调查基础上,论述了泸定县泥石流灾害成因、发生特征、危害和发展趋势,提出了相关防治建议。(1)成因表现为复杂的断裂构造导致流域内松散物源丰富,较大的相对高差提供了良好势能条件,而汛期集中强降雨则提供了动能条件,且雨量条件中当日雨量与前期有效降雨量之间具有幂函数关系; (2)发生特征表现出典型的空间群发性(包括2005-06-30群发性泥石流、2005-08-11群发性泥石流和2006-07-14群发性泥石流)与时间的夜发性; (3)危害方式主要包括淤埋、冲毁、侵蚀、堵河4种,泥石流已造成74人死亡; (4)发展趋势表现为泥石流沟多处于形成期和发展期(113条,占89%),发生的年际准周期由20a缩短至不足10a,且发生条(次)由4条(次)增加至44条次(2005年); (5)泸定县泥石流防治的突出问题表现为城镇泥石流问题、泥石流堵塞主河问题、风景区泥石流问题与冲沟泥石流问题,建议通过科学规划、风险防御体系构建、土木工程治理、监测预警等措施予以防御。 相似文献
72.
Dr. Dinar Abdullin Nico Fleck Christoph Klein Philipp Brehm Sebastian Spicher Prof. Dr. Arne Lützen Prof. Dr. Stefan Grimme Prof. Dr. Olav Schiemann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(10):2586-2596
Iron(III) porphyrins have the propensity to form μ2-oxo-dimers, the structures of which resemble two wheels on an axle. Whereas their crystal structure is known, their solution structure and internal dynamics is not. In the present work, the structure and dynamics of such dimers were studied by means of electron paramagnetic resonance (EPR) spectroscopy and quantum chemistry based molecular dynamics (MD) simulations by using the semiempirical tight-binding method (GFN-xTB). To enable EPR investigation of the dimers, a nitroxide was attached to each of the tetraphenylporphyrin cores through a linear and a bent linker. The inter-nitroxide distance distributions within the dimers were determined by continuous-wave (cw)-EPR and pulsed electron–electron double resonance (PELDOR or DEER) experiments and, with the help of MD, interpreted in terms of the rotation of the porphyrin planes with respect to each other around the Fe–O–Fe axis. It was found that such rotation is restricted to the four registers defined by the phenyl substituents. Within the registers, the rotation angle swings between 30° and 60° in the proximal and between 125° and 145° in the distal register. With EPR, all four angles were found to be equally populated, whereas the 30° and 145° angles are strongly favored to the expense of the 60° and 125° angles in the MD simulation. In either case, the internal dynamics of these dimers thus resemble the motion of a step motor. 相似文献
73.
74.
Reaction of Ni2+ and SnS as a Way to Form Ni@SnS and Sn2Ni3S2 Nanocrystals: Control of Product Formation and Shape 下载免费PDF全文
Stefan Michael Rommel Dr. Richard Weihrich 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9863-9867
Reductive diffusion of Ni2+ into SnS particles was shown to selectively form Sn2Ni3S2, hybrid, or even core‐shell Ni@SnS, Ni1.523Sn, and Ni3S2, by tuning the reaction conditions at low temperatures. The mechanism of Ni2+ reduction and diffusion into SnS was observed in ethylene glycol, which served both as solvent and reducing agent. Tuning of reaction temperature and duration, morphology of the template SnS, and the application of ethylenediamine as supporting chelating agent, influence the formation of the final products. Their formation was controlled by carefully adjusting redox and equilibrium reactions. The products were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive X‐ray spectroscopy analysis (EDX). 相似文献
75.
Gregory S. Pomrehn Alex Zevalkink Wolfgang G. Zeier Axel van de Walle G. Jeffrey Snyder 《Angewandte Chemie (International ed. in English)》2014,53(13):3422-3426
Experimentally, AZn2Sb2 samples (A=Ca, Sr, Eu, Yb) are found to have large charge carrier concentrations that increase with increasing electronegativity of A. Using density functional theory (DFT) calculations, we show that this trend can be explained by stable cation vacancies and the corresponding finite phase width in A1?xZn2Sb2 compounds. 相似文献
76.
The generation of nucleophiles from the combination of aryl boronic acids and catalytic amounts of copper salt allows a reactivity distinct from other organometallic species, such as organolithiums or Grignard reagents. Here we examine how the electronic and steric properties of the boronic acid affect the formation of active nucleophiles and their subsequent reactivity with iminium‐type compounds, showing that electron‐rich substrates display reduced reactivity. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
77.
Dr. Noemi Linares Dr. Erika De Oliveira Jardim Dr. Geetu Sharma Dr. Elena Serrano Prof. Alexandra Navrotsky Prof. Dr. Javier García-Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(43):10045-10048
With the aim of understanding the thermochemistry of the introduction of mesoporosity in zeolites by using surfactants, high temperature oxide melt solution calorimetry was used to determine the change in the enthalpy of formation of USY zeolite before and after the introduction of mesoporosity. Our results confirm that this process only slightly destabilizes the zeolite by the additional surface area. However, this can be overcome by the stabilizing effect of the interactions between the surfactant and the zeolite framework. 相似文献
78.
The first-order thermodynamic perturbation theory of Wertheim (TPT1) is extended to treat ring aggregates, formed by inter- and intramolecular association. The expression for the residual association contribution to the Helmholtz free energy for ring aggregates, incorporating the appropriate terms in Wertheim's fundamental graph sum of the TPT1 density expansion, is derived to calculate the distribution of the molecular bonding states. This requires the introduction of two new parameters to characterise each possible ring type: the ring size τ, which is equal to one in the case of intramolecular association, and a parameter W that captures the likelihood of two ring-forming sites bonding. The resulting framework can be incorporated in equations of state that account for the residual association contribution to the free energy, such as the statistical associating fluid theory (SAFT) family, or the cubic plus association (CPA) equation of state. This extends the applicability of these equations of state to mixtures with an arbitrary number of association sites capable of hydrogen bonding to form intramolecular and intermolecular rings. The formalism is implemented within SAFT-VR Mie to calculate the fluid-phase equilibria of model chain-like molecules containing two associating sites A and B, allowing for the formation of open-chain aggregates and intramolecular bonds. The effect of adding a second component that competes for the association sites that mediate intramolecular association in the chain is also examined. Accounting for intramolecular bonding is shown to have a significant impact on the phase equilibria of such systems. 相似文献
79.
The paper deals with a model that describes a predator–prey system with a common consuming resource. We use Lyapunov functions to prove the global stability of the kinetic system and the diffusive system. The existence of non-constant positive steady state solutions is shown to identify the range of parameters of spatial pattern formation for the cross-diffusion system. 相似文献
80.
The stabilization of partially-premixed jet flames in the presence of high potential electric fields
Numerous research efforts have focused on flame stabilization and emissions. Based on initial experiments, specific mechanisms resulting from DC electric fields were chosen to be investigated, namely the chemical, thermal, and ionization mechanisms. Numerical simulations were performed on premixed propane-ozone-air flames to characterize ozone effects on flame speed resulting from the formation of ozone in high potential electric fields. These results were compared against partially premixed flame experiments to observe the dominant influences within leading edge stabilization within high potential electric fields. It was found that the electromagnetic or ionization influences, serve as the dominant effect on the combustion zone. 相似文献