全文获取类型
收费全文 | 3336篇 |
免费 | 116篇 |
国内免费 | 20篇 |
专业分类
化学 | 2230篇 |
晶体学 | 23篇 |
力学 | 29篇 |
数学 | 458篇 |
物理学 | 732篇 |
出版年
2023年 | 15篇 |
2022年 | 34篇 |
2021年 | 54篇 |
2020年 | 61篇 |
2019年 | 74篇 |
2018年 | 57篇 |
2017年 | 57篇 |
2016年 | 119篇 |
2015年 | 93篇 |
2014年 | 113篇 |
2013年 | 208篇 |
2012年 | 203篇 |
2011年 | 244篇 |
2010年 | 145篇 |
2009年 | 129篇 |
2008年 | 198篇 |
2007年 | 176篇 |
2006年 | 180篇 |
2005年 | 140篇 |
2004年 | 127篇 |
2003年 | 93篇 |
2002年 | 97篇 |
2001年 | 54篇 |
2000年 | 41篇 |
1999年 | 42篇 |
1998年 | 44篇 |
1997年 | 26篇 |
1996年 | 33篇 |
1995年 | 25篇 |
1994年 | 23篇 |
1993年 | 34篇 |
1992年 | 21篇 |
1991年 | 18篇 |
1990年 | 17篇 |
1989年 | 20篇 |
1988年 | 17篇 |
1987年 | 27篇 |
1986年 | 16篇 |
1985年 | 27篇 |
1984年 | 17篇 |
1983年 | 20篇 |
1982年 | 15篇 |
1981年 | 20篇 |
1980年 | 24篇 |
1979年 | 16篇 |
1978年 | 15篇 |
1977年 | 20篇 |
1976年 | 12篇 |
1975年 | 18篇 |
1972年 | 12篇 |
排序方式: 共有3472条查询结果,搜索用时 62 毫秒
61.
The decomposition of N2O in a 13.56-MHz parallel-plate system was studied usingin situ Fourier transform infrared (FTIR) spectroscopy. Areas of two infrared absorption bands of N2O recorded at 8 cm–1 resolution were used to estimate relative gas-phase dissociation as a function of rf power and flow rate at 500 mT. Flow rate was found to strongly affect band areas over the range of powers investigated (10–90 W). The effect of rf power on band areas diminished above 40 W, probably due to poor plasma confinement. Distortion of the band shapes by the plasma permitted rotational temperatures to be estimated. Rotational temperature increased essentially linearly with power at constant flow rate, reaching 450 K at 80 W, but was independent of flow rate at constant power. Rotational temperatures were also found to depend on the temperature of the electrodes, which were heated by plasma exposure. No infrared-active product species were observed even under batch conditions where all N2O was irreversibly dissociated. This lack of detectable products and a 50% pressure rise observed in a batch study suggest that N2 and O2 are the primary stable discharge products. 相似文献
62.
The extraction of Am, Eu, Ce(III), Zr(IV), and Sr from aqueous nitric acid— nitrate media by dibutyl N,N-diethylcarbamylphosphonate
and dibutyl N,N-diethylcar-bamylmethylenephosphonate dissolved in carbon tetrachloride was studied. The trivalent actinide
and lanthanide elements may be separated in certain aqueous phase acidity regions from Fe(III), Zr(IV), and Sr, whereas the
separation of actinide elements from the lanthanide elements is poor. The extractant to metal ratio in the extracted complexes
of Am, Eu, and Ce(III) is 3. The interferences in the extraction due to acidic impurities in the extracting agent are discussed. 相似文献
63.
Expressing the influence of reservoirs (lattice modes, solvent etc.) on the exciton or electron propagation in homogeneous systems via two relaxation times in the Agranovich and Galanin model, the convolutionless Generalized Master Equations for the site occupation probabilities are derived. Two different projection operator techniques are used. Identity of the two approaches is verified for a dimer and physical contents of the result are discussed. 相似文献
64.
The density-matrix renormalization group algorithm has emerged as a promising new method in ab initio quantum chemistry. However, many problems still need to be solved before this method can be applied routinely. At the start of such a calculation, the orbitals originating from a preceding quantum chemical calculation must be placed in a specific order on a one-dimensional lattice. This ordering affects the convergence of the density-matrix renormalization group iterations significantly. In this paper, we present two approaches to obtain optimized orderings of the orbitals. First, we use a genetic algorithm to optimize the ordering with respect to a low total electronic energy obtained at a predefined stage of the density-matrix renormalization group algorithm with a given number of total states kept. In addition to that, we derive orderings from the one- and two-electron integrals of our test system. This test molecule is the chromium dimer, which is known to possess a complicated electronic structure. For this molecule, we have carried out calculations for the various orbital orderings obtained. The convergence behavior of the density-matrix renormalization group iterations is discussed in detail. 相似文献
65.
The mechanism of biological dinitrogen reduction is still unsolved, and the structure of the biological reaction center, the FeMo cofactor with its seven iron atoms bridged by sulfur atoms, is too complicated for direct attack by current sophisticated quantum chemical methods. Therefore, iron-sulfur complexes with biologically compatible ligands are utilized as models for studying particular features of the reduction process: coordination energetics, thermodynamic stability of intermediates, relative stability of isomers of N2H2, end-on versus side-on binding of N2, and the role of states of different multiplicity at a single iron center. From the thermodynamical point of view, the crucial steps are dinitrogen binding and reduction to diazene, while especially the reduction of hydrazine to ammonia is not affected by the transition metal complex, because the complex-free reduction reaction is equally favored. Moreover, the abstraction of coordinated ammonia can be easily achieved and the complex is recovered for the next reduction cycle. Our results are discussed in the light of studies on various model systems in order to identify common features and to arrive at conclusions which are of importance for the biological mechanism. 相似文献
66.
Nanotechnology promises to enhance the functionality and sensitivity of miniaturized analytical systems. For example, nanoscale transport systems, which are driven by molecular motors, permit the controlled movement of select cargo along predetermined paths. Such shuttle systems may enhance the detection efficiency of an analytical system or facilitate the controlled assembly of sophisticated nanostructures if transport can be coordinated through complex track networks. This study determines the feasibility of complex track networks using kinesin motor proteins to actively transport microtubule shuttles along micropatterned surfaces. In particular, we describe the performance of three basic structural motifs: (1) crossing junctions, (2) directional sorters, and (3) concentrators. We also designed track networks that successfully sort and collect microtubule shuttles, pointing the way towards lab-on-a-chip devices powered by active transport instead of pressure-driven or electroosmotic flow. 相似文献
67.
We report the use of a novel pulsed ESR technique for distance measurement, based on the detection of double quantum coherence (DQC), which yields high quality dipolar spectra, to significantly extend the range of measurable distances in proteins using nitroxide spin-labels. Eight T4 lysozyme (T4L) mutants, doubly labeled with methanethiosulfonate spin-label (MTSSL), have been studied using DQC-ESR at 9 and 17 GHz. The distances span the range from 20 A for the 65/76 mutant to 47 A for the 61/135 mutant. The high quality of the dipolar spectra also allows the determination of the distance distributions, the width of which can be used to set upper and lower bounds in future computational strategy. It is also demonstrated that the shape of these distributions can reveal the presence of multiple conformations of the spin-label, an issue of critical relevance to the structural interpretation of the distances. The distances and distributions found in this study are readily rationalized in terms of the known crystal structure, the characteristic conformers of the nitroxide side chains, and molecular modeling. This study sets the stage for the use of DQC-ESR for determining the tertiary structure of large proteins with just a small number of long-distance constraints. 相似文献
68.
Structure Studies on Derivatives of the Nickel Complex Ni(ONO) (ONO2? = Dianion of a Tridentate Schiff Base) The thermodynamically stable form of the solvent free, formally tri-coordinate complex Ni(ONO) (ONO2? = dianion of N-(2-hydroxyphenyl)-2-ethoxycarbonyl-3-ox(o-butene(1) amine(1)) as well as the mono adducts Ni(ONO)X with X = ammonia and X = diphenyl thiourea (DPT) have been characterized by X-ray structure analysis. In all cases the central atom is coordinated in a square-planar fashion, only for the adduct Ni(ONO)(DPT) a pyramidal distortion is observed which is due to the formation of hydrogen bonds. The solvent free form is a dimer [Ni(ONO)]2, and represents one of the few examples of dinuclear nickel complexes with a planar [NO3] coordination. The phenolic O-atoms act as bridging ligands. Due to their reduced π-donor strength the bond lengths Ni? O trans to the bridges are significantly shortened. In contrast to the analogous complex with an aliphatic bridge, “NiEIA”, both halves of the dimeric molecules are coplanar with a Ni? Ni distance of 3.29 Å. 相似文献
69.
Subhash Deshmukh Wayne P. Hess 《Journal of photochemistry and photobiology. A, Chemistry》1994,80(1-3):17-21
Jet-cooled phosphorus trichloride, carbon tetrachloride, chloroform and molecular chlorine are photodissociated in the UV wavelength range 235–238 nm. Chlorine atom photofragments Cl (2P3/2) and Cl* (2P1/2) are detected via resonance-enhanced (2+1) ionization throughout the 232–238 nm wavelength region. The relative Cl* yields, φ*=[Cl*]/([Cl]+[Cl*]), are measured for both 35Cl and 37Cl isotopes using the two-photon atomic transitions at 235.3 nm for Cl and 237.8 nm for Cl*. Preliminary results indicate that the Cl* yields are different for the two isotopes for some of the precursors. In addition, we obtained the two-photon oscillator strength of the Cl transition at 237.7 nm relative to the Cl* transition at 237.8 nm. The advantage of using the two-photon Cl transition at 237.7 nm for quantum yield measurements is discussed. 相似文献
70.
The abilities of both 2,2,6,6-tetramethylpiperidine (I) and its nitroxyl (II) to trap radicals involved in hydrocarbon photo-oxidations have been studied in cumene and 1,3,5-trimethylcyclohexane at 27° using AIBN, hydroperoxide and dialkylperoxide as initiators: the light was either the band 300–400 nm or 366 nm. Under conditions of photolysis of ROOH (degenerate branching), I is oxidized to II. II is capable of trapping R' radicals, the rate constant being ~50 times lower than that for RO.2 formation. RO.2 radicals react with neither I nor II. Under the condition of degenerate branching, II is capable of intercepting the radical fragments from decomposing hydroperoxide. The rate constant of this process is ~500 times higher than that for hydrogen abstraction by these fragments. A reaction mechanism is suggested: hydrogen bonded associates formed between an N-containing stabilizer and ROOH play a dominant role. The principal intermediates in this mechanism are represented by >NO., >NOH and >NOR species. 相似文献