全文获取类型
收费全文 | 2720篇 |
免费 | 113篇 |
国内免费 | 7篇 |
专业分类
化学 | 2129篇 |
晶体学 | 7篇 |
力学 | 41篇 |
数学 | 393篇 |
物理学 | 270篇 |
出版年
2023年 | 21篇 |
2022年 | 76篇 |
2021年 | 94篇 |
2020年 | 71篇 |
2019年 | 76篇 |
2018年 | 37篇 |
2017年 | 42篇 |
2016年 | 110篇 |
2015年 | 96篇 |
2014年 | 103篇 |
2013年 | 167篇 |
2012年 | 196篇 |
2011年 | 201篇 |
2010年 | 153篇 |
2009年 | 113篇 |
2008年 | 169篇 |
2007年 | 150篇 |
2006年 | 136篇 |
2005年 | 136篇 |
2004年 | 130篇 |
2003年 | 103篇 |
2002年 | 99篇 |
2001年 | 35篇 |
2000年 | 43篇 |
1999年 | 31篇 |
1998年 | 25篇 |
1997年 | 26篇 |
1996年 | 30篇 |
1995年 | 21篇 |
1994年 | 22篇 |
1993年 | 18篇 |
1992年 | 21篇 |
1991年 | 8篇 |
1990年 | 5篇 |
1989年 | 5篇 |
1988年 | 7篇 |
1987年 | 10篇 |
1986年 | 8篇 |
1985年 | 7篇 |
1983年 | 5篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1970年 | 2篇 |
1909年 | 3篇 |
排序方式: 共有2840条查询结果,搜索用时 15 毫秒
181.
The formation and stability of some carboxylate and hydroxycarboxylate (acetate, 1,2,3-propanetricarboxylate, 1,2,3,4-butanetetracarboxylate, malate and citrate) complexes of monomethyltin trichloride was studied potentiometrically at 25 degrees C and at different ionic strengths in NaNO3 aqueous solution. The following quite stable species are formed in the different systems (M = CH3Sn3+): ML(OH)+, ML2(OH)0, ML(OH)2(0) and M2L(OH)5(0) for acetate; MLH+, ML0, ML(OH)- and ML(OH)2(2-) for propanetricarboxylate; MLH2+, MLH0, ML-, ML(OH)2- and ML(OH)2(3-) for butanetetracarboxylate; ML(OH)0, ML(OH)2- and ML(OH)3(2-) for malate; ML0, ML(OH)-, ML(OH)2(2-) and ML(OH)3(3-) for citrate. Hydroxycarboxylate complexes are significantly stronger than simple carboxylate ones and this is likely to be due to the interaction of the -OH group in citrate and malate with monomethyltin(IV), whose strength was also quantified. It was found that the stability of these complexes can be roughly expressed by the simple relationship log K = a zeta, where zeta is the product of the charges of reactants and log K is the equilibrium constant. For simple carboxylic ligands we have a = 1.8 +/- 0.4 and, for hydroxycarboxylic ligands, a = 3.7 +/- 0.9. Other useful empirical relationships are reported. Moreover, hydroxycarboxylic complexes also play a prominent role in the speciation of monomethyltin(IV) under the pH conditions of interest for natural fluids. 相似文献
182.
More specific official methodology is needed to survey the illegal use of clenbuterol in animal production plus the synthesis of new compounds that currently elude routine analytical methods. The identification of a new adrenergic agonist, N1-(2-(4-amino-3,5-dichlorophenyl)-2-hydroxyethyl)-N1-isopropyl-propanamide (known as compound A) in animal feed has prompted studies to verify if the existing cleanup procedures developed for clenbuterol are really effective. This study considers the ion-exchange mechanism on cyanopropyl (CN), sulfonic cation exchange (SCX), mixed phase (MPH) (C8 + SCX), and nonendcapped C18 (C18NE) solid-phase extraction (SPE) columns. Results indicate that compound A (by contrast with clenbuterol) is not efficiently retained on the CN, SCX, and MPH SPE columns (recovery <10%). This finding thus leads to the development of a gas chromatography-tandem mass spectrometry procedure based on C18NE SPE that is able to purify both agonists from bovine livers spiked at 0.5, 1.0, and 2.0 ppb with a mean recovery of 93% for clenbuterol and 92% for compound A. 相似文献
183.
Morilla ME Morfes G Nicasio MC Belderrain TR Mar Díaz-Requejo M Graiff C Tiripicchio A Sánchez-Delgado R Pérez PJ 《Chemical communications (Cambridge, England)》2002,(17):1848-1849
N,N, N',N'-Tetraethylethylenediamine undergoes simple or double intramolecular dealkylation reactions in the presence of the complexes [RuCl2(diene)]n (diene = cod, nbd) or trans-[RuCl2(diene)(morfoline)2 at 80 degrees C to afford chelating amine ligands which contains one or two N-H functionalities. 相似文献
184.
The dissociative adsorption of H2 on the Si(001) surface is theoretically investigated for several reaction pathways using quantum Monte Carlo methods. Our reaction energies and barriers are at large variance with those obtained with commonly used approximate exchange-correlation density functionals. Our results for adsorption support recent experimental findings, while, for desorption, the calculations give barriers in excess of the presently accepted experimental value, pinpointing the role of coverage effects and desorption from steps. 相似文献
185.
We present an ab initio study of the optical absorption spectra of isolated as well as crystalline trans-polyacetylene. We include excitonic effects by solving the Bethe-Salpeter equation for the electron-hole two-particle correlation function. We observe that the strength of the electron-hole interactions drastically reduces when going from an isolated polymer chain to a crystalline arrangement. This is not only a result of enhanced screening in the 3D material, but also of the increased spatial extent of the exciton perpendicular to the polymer chains. We point out that these findings apply to crystalline phases of conjugated polymers and molecular crystals in general. 相似文献
186.
We report on ab-initio frozen-phonon calculations for the five A1g
Raman-active-modes of YBa2Cu3O7 atq=0. The determination of the equilibrium positions of the atoms Ba, Cu(2), O(2), O(3), O(4) as well as of phonon frequencies
and respective eigenvectors is based on the calculation of atomic forces within the LAPW-method. The general agreement between
our results and experimental structural data and phonon frequencies is good. Deviations are discussed in connection with the
local-density approximation. 相似文献
187.
188.
A polymer-supported diketone was synthesized and used to fully protect/mask primary amines by the formation of a pyrrole ring. Various reactions can be performed on this system which then can be cleaved with full restoration of the amine functionality. The resin can also be recycled at least once without loss of purity of the final compound. [structure: see text] 相似文献
189.
We introduce an efficient lattice regularization scheme for quantum Monte Carlo calculations of realistic electronic systems. The kinetic term is discretized by a finite difference Laplacian with two mesh sizes, a and a', chosen so that the electrons can diffuse in a configuration space which is in practice indistinguishable from the continuum, and the different length scales in the system can be efficiently taken in account. The regularized Hamiltonian goes to the continuous limit for a --> 0 and allows the inclusion of nonlocal potentials in a consistent variational scheme, substantially improving the accuracy upon previous nonvariational approaches. 相似文献
190.
It is shown that the model of perfectly reflecting boundaries widely employed in cavity QED is unsuitable for systems that have long-wavelength excitations. A prime example is a free charged particle near a reflecting wall. Modeling the wall as perfectly reflecting from the outset ignores evanescent waves that couple to the particle through virtual excitations at low energies, which can lead to errors in order of magnitude and even sign. The example of a free electron near an imperfectly reflecting wall characterized by a constant frequency-independent refractive index n is investigated in detail by determining its energy shift relative to an electron in vacuum through both nonrelativistic and relativistic calculations. 相似文献