全文获取类型
收费全文 | 809篇 |
免费 | 35篇 |
国内免费 | 2篇 |
专业分类
化学 | 522篇 |
晶体学 | 4篇 |
力学 | 11篇 |
数学 | 99篇 |
物理学 | 210篇 |
出版年
2023年 | 6篇 |
2022年 | 15篇 |
2021年 | 16篇 |
2020年 | 30篇 |
2019年 | 26篇 |
2018年 | 13篇 |
2017年 | 12篇 |
2016年 | 13篇 |
2015年 | 31篇 |
2014年 | 21篇 |
2013年 | 32篇 |
2012年 | 38篇 |
2011年 | 31篇 |
2010年 | 24篇 |
2009年 | 13篇 |
2008年 | 31篇 |
2007年 | 33篇 |
2006年 | 35篇 |
2005年 | 35篇 |
2004年 | 28篇 |
2003年 | 13篇 |
2002年 | 19篇 |
2001年 | 11篇 |
2000年 | 12篇 |
1999年 | 15篇 |
1998年 | 18篇 |
1997年 | 7篇 |
1996年 | 11篇 |
1995年 | 8篇 |
1994年 | 16篇 |
1993年 | 18篇 |
1992年 | 15篇 |
1991年 | 6篇 |
1990年 | 6篇 |
1988年 | 6篇 |
1987年 | 8篇 |
1986年 | 9篇 |
1985年 | 11篇 |
1984年 | 8篇 |
1983年 | 12篇 |
1982年 | 5篇 |
1981年 | 9篇 |
1980年 | 7篇 |
1979年 | 16篇 |
1978年 | 11篇 |
1977年 | 8篇 |
1976年 | 12篇 |
1975年 | 7篇 |
1974年 | 10篇 |
1972年 | 5篇 |
排序方式: 共有846条查询结果,搜索用时 15 毫秒
81.
We investigate the problem of packing identical hard objects on regular lattices in d dimensions. Restricting configuration space to parallel alignment of the objects, we study the densest packing at a given aspect ratio X. For rectangles and ellipses on the square lattice as well as for biaxial ellipsoids on a simple cubic lattice, we calculate the maximum packing fraction φ(d)(X). It is proved to be continuous with an infinite number of singular points X(ν)(min), X(ν)(max), ν = 0, ±1, ±2,…. In two dimensions, all maxima have the same height, whereas there is a unique global maximum for the case of ellipsoids. The form of φ(d)(X) is discussed in the context of geometrical frustration effects, transitions in the contact numbers, and number-theoretical properties. Implications and generalizations for more general packing problems are outlined. 相似文献
82.
Tristan J. Keller Christopher Sterzenbach Joshua Bahr Taria L. Schneiders Markus Bursch Julia Kohn Theresa Eder John M. Lupton Stefan Grimme Sigurd Hger Stefan-S. Jester 《Chemical science》2021,12(27):9352
Molecular spoked wheels with D3h and Cs symmetry are synthesized by Vollhardt trimerization of C2v-symmetric dumbbell structures with central acetylene units and subsequent intramolecular ring closure. Scanning tunneling microscopy of the D3h-symmetric species at the solid/liquid interface on graphite reveals triporous chiral honeycomb nanopatterns in which the alkoxy side chains dominate the packing over the carboxylic acid groups, which remain unpaired. In contrast, Cs-symmetric isomers partially allow for pairing of the carboxylic acids, which therefore act as a probe for the reduced alkoxy chain nanopattern stabilization. This observation also reflects the adsorbate substrate symmetry mismatch, which leads to an increase of nanopattern complexity and unexpected templating of alkoxy side chains along the graphite armchair directions. State-of-the-art GFN-FF calculations confirm the overall structure of this packing and attribute the unusual side-chain orientation to a steric constraint in a confined environment. These calculations go far beyond conventional simple space-filling models and are therefore particularly suitable for this special case of molecular packing.Scanning tunneling microscopy investigations of phenylene-based molecular spoked wheels with D3h and Cs symmetries on graphite show the competitive or complementary effects of carboxylic acid groups and alkoxy chains on the nanopattern formation. 相似文献
83.
We obtain a representation for set-valued risk measures which are defined on the completed \(l\) -tensor product \(E\widetilde{\otimes }_l G\) of Banach lattices \(E\) and \(G\) . This representation extends known representations for set-valued risk measures defined on Bochner spaces \(L^p(\mathbb {P}, \mathbb {R}^d)\) of \(p\) -integrable functions with values in \(\mathbb {R}^d\) . 相似文献
84.
We consider generalizations of Schützenberger’s promotion operator on the set $\mathcal{L}$ of linear extensions of a finite poset of size n. This gives rise to a strongly connected graph on $\mathcal{L}$ . By assigning weights to the edges of the graph in two different ways, we study two Markov chains, both of which are irreducible. The stationary state of one gives rise to the uniform distribution, whereas the weights of the stationary state of the other have a nice product formula. This generalizes results by Hendricks on the Tsetlin library, which corresponds to the case when the poset is the anti-chain and hence $\mathcal{L}=S_{n}$ is the full symmetric group. We also provide explicit eigenvalues of the transition matrix in general when the poset is a rooted forest. This is shown by proving that the associated monoid is $\mathcal {R}$ -trivial and then using Steinberg’s extension of Brown’s theory for Markov chains on left regular bands to $\mathcal {R}$ -trivial monoids. 相似文献
85.
86.
Under irradiation metastable quasicrystals undergo a phase transition to an amorphous state. This transition can be reversed by annealing. As in normal crystalline materials the phase transition is considered to be triggered by generation and recombination of vacancies and interstitial atoms (Frenkel pairs). We have classified the possible Frenkel defects in a metastable monatomic quasicrystal with respect to geometric and energetic properties. With numerical simulation we have studied the behaviour of the quasicrystal under a load of Frenkel defects for various defect concentrations. We find three ranges of behaviour: up to 5% defects per atom the structure remains icosahedral, in a middle range it stays disordered icosahedral or it becomes either disordered or perfect crystalline, depending on the implementation of the defects. If there are more than 10% defects the structure becomes irreversibly amorphous. We finally compare our results with experimental data. 相似文献
87.
P. Gippner K. D. Schilling W. Seidel F. Stary E. Will H. Sodan S. M. Lukyanov V. S. Salamatin Yu. E. Penionzhkevich G. G. Chubarian R. Schmidt 《Zeitschrift für Physik A Hadrons and Nuclei》1986,325(3):335-346
Fragment mass distributions are presented obtained in the heavy-ion reactions22Ne+249Cf,32S+238U,40Ar+232Th and56Fe+208Pb leading to composite systems with equal nuclear charge numberZ=108. The experiments were performed at the heavy-ion cyclotron U 300 of the Laboratory of Nuclear Reactions in Dubna. The spectrometer DEMAS was used to measure the time-of-flight values and the laboratory angles of the correlated fragments. The shape of the mass distributions strongly depends on the initial mass asymmetry. When decreasing the bombarding energy down to values near the Coulomb barrier, the mass distributions obtained in the reactions32S+238U and40Ar+232Th exhibit relative maxima ofM≈205 interpreted to be due to stabilizing effects of nuclear shells during the fragmentation process. 相似文献
88.
Above a certain density threshold, suspensions of rodlike colloidal particles form system-spanning networks. Using Monte Carlo simulations, we investigate how the depletion forces caused by spherical particles affect these networks in isotropic suspensions of rods. Although the depletion forces are strongly anisotropic and favor alignment of the rods, the percolation threshold of the rods decreases significantly. The relative size of the effect increases with the aspect ratio of the rods. The structural changes induced in the suspension by the depletant are characterized in detail and the system is compared to an ideal fluid of freely interpenetrable rods. 相似文献
89.
Prof. Dr. Holger Braunschweig Theresa Dellermann Dr. William C. Ewing Thomas Kramer Christoph Schneider Stefan Ullrich 《Angewandte Chemie (International ed. in English)》2015,54(35):10271-10275
The syntheses of sulfur‐ and selenium‐bridged cyclic compounds containing boron stabilized by N‐heterocyclic carbenes (NHCs) have been achieved by the reductive insertion of elemental chalcogens into boron–boron multiple bonds. The three pairs of bonding electrons between the boron atoms in the triply bonded diboryne enabled six‐electron reduction reactions, resulting in the formation of [2.2.1]‐bicyclic systems wherein bridgehead boron atoms are spanned by three chalcogen bridges. A similar reaction using a diborene (boron–boron double bond) resulted in the reductive transfer of both pairs of bonding electrons to three sulfur atoms, yielding a NHC‐stabilized trisulfidodiborolane. The demonstration of these six‐ and four‐electron reductions lends support to the presence of three and two pairs of bonding electrons between the boron atoms of the diboryne and diborene, respectively, a fact that may be useful in future discussions on bond order. 相似文献
90.
The Synthesis of B2(SIDip)2 and its Reactivity Between the Diboracumulenic and Diborynic Extremes
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Julian Bhnke Holger Braunschweig Theresa Dellermann William C. Ewing Kai Hammond J. Oscar C. Jimenez‐Halla Thomas Kramer Jan Mies 《Angewandte Chemie (International ed. in English)》2015,54(46):13801-13805
A new compound with the formula L‐B2‐L wherein the stabilizing ligand (L) is 1,3‐bis[diisopropylphenyl]‐4,5‐dihydroimidazol‐2‐ylidene (SIDip) has been synthesized, isolated, and characterized. The π‐acidity of the SIDip ligand, intermediate between the relatively non‐acidic IDip (1,3‐bis[diisopropylphenyl]imidazol‐2‐ylidene) ligand and the much more highly acidic CAAC (1‐[2,6‐diisopropylphenyl]‐3,3,5,5‐tetramethylpyrrolidin‐2‐ylidene) ligand, gives rise to a compound with spectroscopic, electrochemical, and structural properties between those of L‐B2‐L compounds stabilized by CAAC and IDip. Reactions of all three L‐B2‐L compounds with CO demonstrate the differences caused by their respective ligands, as the π‐acidities of the CAAC and SIDip carbenes enabled the isolation of bis(boraketene) compounds (L(OC)B‐B(CO)L), which could not be isolated from reactions with B2(IDip)2. However, only B2(IDip)2 and B2(SIDip)2 could be converted into bicyclic bis(boralactone) compounds. 相似文献