全文获取类型
收费全文 | 3169篇 |
免费 | 651篇 |
国内免费 | 277篇 |
专业分类
化学 | 741篇 |
晶体学 | 35篇 |
力学 | 271篇 |
综合类 | 38篇 |
数学 | 778篇 |
物理学 | 2234篇 |
出版年
2024年 | 4篇 |
2023年 | 55篇 |
2022年 | 67篇 |
2021年 | 49篇 |
2020年 | 103篇 |
2019年 | 76篇 |
2018年 | 74篇 |
2017年 | 85篇 |
2016年 | 113篇 |
2015年 | 99篇 |
2014年 | 148篇 |
2013年 | 232篇 |
2012年 | 171篇 |
2011年 | 231篇 |
2010年 | 204篇 |
2009年 | 256篇 |
2008年 | 228篇 |
2007年 | 241篇 |
2006年 | 203篇 |
2005年 | 166篇 |
2004年 | 202篇 |
2003年 | 141篇 |
2002年 | 162篇 |
2001年 | 99篇 |
2000年 | 101篇 |
1999年 | 91篇 |
1998年 | 86篇 |
1997年 | 58篇 |
1996年 | 34篇 |
1995年 | 35篇 |
1994年 | 39篇 |
1993年 | 33篇 |
1992年 | 24篇 |
1991年 | 11篇 |
1990年 | 17篇 |
1989年 | 14篇 |
1988年 | 16篇 |
1987年 | 10篇 |
1986年 | 13篇 |
1985年 | 21篇 |
1984年 | 15篇 |
1983年 | 6篇 |
1982年 | 8篇 |
1981年 | 14篇 |
1980年 | 6篇 |
1979年 | 10篇 |
1978年 | 7篇 |
1977年 | 7篇 |
1976年 | 4篇 |
1975年 | 3篇 |
排序方式: 共有4097条查询结果,搜索用时 31 毫秒
41.
We prove that Gibbs states for the Hamiltonian
, with thes
x varying on theN-dimensional unit sphere, obtained with nonrandom boundary conditions (in a suitable sense), are almost surely rotationally invariant if
withJ
xy i.i.d. bounded random variables with zero average, 1 in one dimension, and 2 in two dimensions. 相似文献
42.
We describe the topology, structure, and stability of giant fullerenes exhibiting various symmetries (I, I
h
, D
2h
, T). Our results demonstrate that it is possible to create two new families of nested chiral icosahedral (I) fullerenes namely C260@C560@C980@C1520@, ...,and C140@C380@C740@C1220@ ..., which exhibit interlayer separations of ca. 3.4 Å. These chiral fullerenes are thought to possess metalliclike conduction properties. We discuss in detail the transformation of polyhedral graphitic particles into quasispherical nested giant fullerenes by reorganization of carbon atoms, which result in the formation of additional pentagonal and heptagonal carbon rings. These spherical structures are metastable and we believe they could be formed under extreme conditions, such as those produced by high-energy electron irradiation. There is circumstantial experimental evidence for the presence of heptagonal rings within these spherical fullerenes. 相似文献
43.
44.
A new class of low melting liquid crystalline octaalkyloxyporphyrins have been synthesised. Their Zn(II)-complexes display an interesting ligation behaviour towards amines (of varying shapes and sizes), ascribed to the steric hindrance or hydrophobic pockets on both the faces of the porphryin as evidenced from the crystal structure of Zn(II)-octabutyloxyporphyrin. 相似文献
45.
Ruiz E Rodríguez-Fortea A Cano J Alvarez S Alemany P 《Journal of computational chemistry》2003,24(8):982-989
The application of theoretical methods based on the density functional theory with hybrid functionals provides good estimates of the exchange coupling constants for polynuclear transition metal complexes. The accuracy is similar to that previously obtained for dinuclear compounds. We present test calculations on simple model systems based on H. He and CH(2). He units to compare with Hartree-Fock and multiconfigurational results. Calculations for complete, nonmodeled polynuclear transition metal complexes yield coupling constants in very good agreement with available experimental data. 相似文献
46.
Jean Bricmont Joel L. Lebowitz Christian Maes 《Journal of statistical physics》1987,48(5-6):1249-1268
We derive a number of new results for correlated nearest neighbor site percolation onZ
d. We show in particular that in three dimensions the strongly correlated massless harmonic crystal, i.e., the Gaussian random field with mean zero and covariance –, has a nontrivial percolation behavior: sites on whichS
x
h percolate if and only ifh
c
. with0
c
< . This provides the first rigorous example of a percolation transition in a system with infinite susceptibility. 相似文献
47.
Nimrod Megiddo 《Mathematical Programming》1986,35(2):140-172
In this paper we analyze the average number of steps performed by the self-dual simplex algorithm for linear programming, under the probabilistic model of spherical symmetry. The model was proposed by Smale. Consider a problem ofn variables withm constraints. Smale established that for every number of constraintsm, there is a constantc(m) such that the number of pivot steps of the self-dual algorithm,(m, n), is less thanc(m)(lnn)
m(m+1)
. We improve upon this estimate by showing that(m, n) is bounded by a function ofm only. The symmetry of the function inm andn implies that(m, n) is in fact bounded by a function of the smaller ofm andn.
Parts of this research were done while the author was visiting Stanford University, XEROX- PARC, Carnegie-Mellon University and Northwestern University and was supported in part by the National Science Foundation under Grants MCS-8300984, ECS-8218181 and ECS-8121741. 相似文献
48.
Masaaki Omote 《Tetrahedron letters》2005,46(2):319-322
A new axially dissymmetric ligand with large perfluoroalkyl groups, 2,2′-bis(1-hydroxy-1H-perfluorooctyl)biphenyl (1c), which could not be obtained by the coupling reaction of the aryl bromide using copper powder, was synthesized successfully by the coupling reaction using Ni(COD)2. This ligand showed much higher asymmetric induction in the reaction of diethylzinc with benzaldehyde than the trifluoromethyl (1a) or pentafluoroethyl (1b) analogues. 相似文献
49.
Michael Eyer Karl Schlögl Michael Widhalm 《Monatshefte für Chemie / Chemical Monthly》1984,115(12):1429-1442
Chiral title compounds have been resolved by medium pressure liquid chromatography (MPLC) on triacetylcellulose in ethanol. Whereas a quantitative separation was achieved for16 and20, a recycling technique had to be applied to1,4,6,10 and15 leading to a 100% e.e. for1,6 and15 and to ca. 60% e.e. for4 and10.An unambiguous assignment of the chirality (+)-(R)
a
-(S)
m
for tricarbonylchromium-6,6-dimethyl-diphenicacid dimethylester (4) was deduced both from the photochemical decomplexation to (-)-5 with the known chirality (R)
a
(whose e.e. was determined by MPLC on triacetylcellulose) and by comparison of the1H-n.m.r. spectra of4 and5 thereby proving the structure 4 for the former.Other chiralities both for mono and bis(tricarbonylchromium)biphenyl complexes were established by chemical correlations and comparison of the CD spectra with those of key compounds.
Herrn Prof. Dr.H. Tuppy mit besten Wünschen zum 60. Geburtstag gewidmet. 相似文献
50.
The syntheses of several differently substituted amides formally derived from a chiral amine, either E-2-(2-hydroxyphenyl)cinnamic acid or both E- and Z-2-(2-hydroxynaphthyl)cinnamic acid, are reported. These molecules display a restricted rotation about the C2-Caryl bond. The barriers to rotation about the C2-Caryl bond were measured by the dynamic 1H NMR and were found to vary between 11.8 and 24.5 kcal mol−1, depending on the substitution. In particular, E-2-(2-hydroxynapthyl)cinnamic amides, displayed a high barrier to rotation (ΔGc‡=24.4 kcal mol−1) and could be isolated in both diastereomerically pure forms at room temperature. The X-ray structure of one E-2-(2-hydroxynapthyl)cinnamic amide, was resolved, enabling for the determination of the absolute configuration of the chiral axis (aR). 相似文献