全文获取类型
收费全文 | 32919篇 |
免费 | 252篇 |
国内免费 | 287篇 |
专业分类
化学 | 13862篇 |
晶体学 | 278篇 |
力学 | 1433篇 |
综合类 | 12篇 |
数学 | 9404篇 |
物理学 | 8469篇 |
出版年
2023年 | 36篇 |
2022年 | 137篇 |
2021年 | 221篇 |
2020年 | 136篇 |
2019年 | 161篇 |
2018年 | 1307篇 |
2017年 | 1538篇 |
2016年 | 867篇 |
2015年 | 704篇 |
2014年 | 598篇 |
2013年 | 930篇 |
2012年 | 3429篇 |
2011年 | 2614篇 |
2010年 | 2005篇 |
2009年 | 1690篇 |
2008年 | 803篇 |
2007年 | 889篇 |
2006年 | 835篇 |
2005年 | 4615篇 |
2004年 | 4079篇 |
2003年 | 2439篇 |
2002年 | 593篇 |
2001年 | 327篇 |
2000年 | 134篇 |
1999年 | 207篇 |
1998年 | 152篇 |
1997年 | 94篇 |
1996年 | 76篇 |
1995年 | 56篇 |
1994年 | 66篇 |
1993年 | 41篇 |
1992年 | 188篇 |
1991年 | 165篇 |
1990年 | 143篇 |
1989年 | 111篇 |
1988年 | 106篇 |
1987年 | 66篇 |
1986年 | 42篇 |
1985年 | 45篇 |
1984年 | 43篇 |
1979年 | 34篇 |
1976年 | 84篇 |
1975年 | 39篇 |
1974年 | 40篇 |
1973年 | 49篇 |
1972年 | 40篇 |
1970年 | 35篇 |
1969年 | 37篇 |
1968年 | 36篇 |
1966年 | 37篇 |
排序方式: 共有10000条查询结果,搜索用时 109 毫秒
991.
Unraveling σ and π Effects on Magnetic Anisotropy in cis‐NiA4B2 Complexes: Magnetization,HF‐HFEPR Studies,First‐Principles Calculations,and Orbital Modeling
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Gaëlle Charron Dr. Elena Malkin Dr. Guillaume Rogez Dr. Luke J. Batchelor Dr. Sandra Mazerat Dr. Régis Guillot Dr. Nathalie Guihéry Dr. Anne‐Laure Barra Dr. Talal Mallah Dr. Hélène Bolvin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(47):16850-16862
By using complementary experimental techniques and first‐principles theoretical calculations, magnetic anisotropy in a series of five hexacoordinated nickel(II) complexes possessing a symmetry close to C2v, has been investigated. Four complexes have the general formula [Ni(bpy)X2]n+ (bpy=2,2′‐bipyridine; X2=bpy ( 1 ), (NCS?)2 ( 2 ), C2O42? ( 3 ), NO3? ( 4 )). In the fifth complex, [Ni(HIM2‐py)2(NO3)]+ ( 5 ; HIM2‐py=2‐(2‐pyridyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazolyl‐1‐hydroxy), which was reported previously, the two bpy bidentate ligands were replaced by HIM2‐py. Analysis of the high‐field, high‐frequency electronic paramagnetic resonance (HF‐HFEPR) spectra and magnetization data leads to the determination of the spin Hamiltonian parameters. The D parameter, corresponding to the axial magnetic anisotropy, was negative (Ising type) for the five compounds and ranged from ?1 to ?10 cm?1. First‐principles SO‐CASPT2 calculations have been performed to estimate these parameters and rationalize the experimental values. From calculations, the easy axis of magnetization is in two different directions for complexes 2 and 3 , on one hand, and 4 and 5 , on the other hand. A new method is proposed to calculate the g tensor for systems with S=1. The spin Hamiltonian parameters (D (axial), E (rhombic), and gi) are rationalized in terms of ordering of the 3 d orbitals. According to this orbital model, it can be shown that 1) the large magnetic anisotropy of 4 and 5 arises from splitting of the eg‐like orbitals and is due to the difference in the σ‐donor strength of NO3? and bpy or HIM2‐py, whereas the difference in anisotropy between the two compounds is due to splitting of the t2g‐like orbitals; and 2) the anisotropy of complexes 1 – 3 arises from the small splitting of the t2g‐like orbitals. The direction of the anisotropy axis can be rationalized by the proposed orbital model. 相似文献
992.
Andreiy A. Gushchin Vladimir I. Grinevich Valeriy Ya. Shulyk Elena Yu. Kvitkova Vladimir V. Rybkin 《Plasma Chemistry and Plasma Processing》2018,38(1):123-134
The processes of degradation of 2,4-dichlorophenol (2,4-DCP) aqueous solutions under the action of atmospheric pressure of DBD in oxygen were studied. The degradation of 2,4-DCP proceeds efficiently, the degree of decomposition reaching 100%. The degradation kinetics of 2,4-DCP obeys a formal first-order kinetic law on concentration of 2,4-DCP. The effective rate constants depend weakly on the experimental conditions and are equal to ~ 2 s?1. Based on experimental data, the energy efficiency of 2,4-DCP decomposition was determined to be in the range of 0.039–0.173 molecules per 100 eV depending on the experimental conditions. The composition of the products was studied by gas chromatography, chromatography-mass spectrometry, UV/visible spectroscopy, fluorescent methods and some chemical methods. The main decomposition products present in the solution were found to be carboxylic acids, aldehydes and chloride ions, whereas carbon dioxide and molecular chlorine appear in the gas. The results obtained are compared with similar data from other advanced oxidation processes (AOP’s) methods. 相似文献
993.
Allocation rules for cooperative games can be manipulated by coalitions merging into single players, or, conversely, players splitting into a number of smaller units. This paper collects some (im)possibility results on merging- and splitting-proofness of (core) allocation rules for cooperative games with side-payments. 相似文献
994.
An approach to evaluate the second-order exchange-induction energies of symmetry-adapted intermolecular perturbation theory (SAPT) for single-determinant ground-state monomer wavefunctions has been derived. This approach is correct to all orders of the intermonomer overlap, that is, it takes multiple electron exchange between the monomers into account. The resulting formulae can be written in a compact way and implemented efficiently. Here, the method is employed to investigate the performance of the S 2- or single-exchange approximation at the Hartree-Fock-SAPT level. The list of test systems comprises the prototypical van der Waals- and hydrogen-bridge complexes Ne2, Ar–HF, and (H2O)2, but also the systems HeCl?, NeNa+ and Li+F? involving closed-shell ions. It was found that the errors introduced by the S 2-approximation are more pronounced for the second-order exchange-induction energy than for the first-order exchange energy. While these errors tend to be negligible throughout the well region of complexes such as the neon dimer, they start to be significant in the repulsive part of the well regions of systems such as the water dimer, and in particular for the ionic lithium fluoride molecule. The consequences of these findings for the Hartree-Fock level estimate of higher-order induction plus exchange-induction energies, which is frequently employed in SAPT are also discussed. 相似文献
995.
996.
Elena V. Khoroshilova 《Optimization Letters》2013,7(6):1193-1214
The paper presents a method for solving optimal control problem with free right end and linear differential equations constraints. The proposed iterative process of extragradient-type is formulated in the functional subspace of piecewise continuous controls of L 2. The convergence of the method is proved. 相似文献
997.
Rafa? Janus Piotr Natkański Anna Wach Marek Drozdek Zofia Piwowarska Pegie Cool Piotr Ku?trowski 《Journal of Thermal Analysis and Calorimetry》2012,110(1):119-125
Thermogravimetry, diffuse reflectance infrared Fourier transform spectroscopy, and X-ray photoelectron spectroscopy (XPS) were used for the studying of thermally induced structural changes of polyacrylonitrile (PAN) deposited on the surface of SBA-15 type mesoporous silica. Polymer was introduced onto the support by the precipitation polymerization of acrylonitrile in aqueous suspension of SBA-15. Low temperature transformation (to 723?K) of the deposited PAN was analyzed. It was found that at about 523?K, exothermic cyclization of polymer chains to the so-called ladder form of PAN occurred. However, the total cyclization of PAN required higher carbonization temperatures, at which gradual dehydrogenation followed by graphitization was initiated. XPS revealed that the cyclic form of PAN and a relatively large amount of carbonyl species, formed during the carbonization of the PAN/SBA-15 composite at 623?K, were responsible for the high sorption capacity in the methyl?Cethyl ketone (MEK) vapor elimination. The efficiency in the MEK adsorption was also influenced by the content of PAN-derived carbon deposited on the SBA-15 surface. 相似文献
998.
Elena Akhmatskaya José M. Asua 《Journal of polymer science. Part A, Polymer chemistry》2012,50(7):1383-1393
Modification of the polymer–polymer interfacial tension is a way to tailor‐make particle morphology of waterborne polymer–polymer hybrids. This allows achieving a broader spectrum of application properties and maximizing the synergy of the positive properties of both polymers, avoiding their drawbacks. In situ formation of graft copolymer during polymerization is an efficient way to modify the polymer–polymer interfacial tension. Currently, no dynamic model is available for polymer–polymer hybrids in which a graft copolymer is generated during polymerization. In this article, a novel model based on stochastic dynamics is developed for predicting the dynamics of the development of particle morphology for composite waterborne systems in which a graft copolymer is produced in situ during the process. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
999.
State-of-the-art compact recirculating electron accelerators operating at intermediate energies (tens of MeV) are reviewed. The acceleration schemes implemented in the rhodotron, ridgetron, fantron, and cylindertron machines are discussed. Major accelerator components such as the electron guns, accelerating cavities, and bending magnets are described. The parameters of currently operating recirculating accelerators are tabulated, and applications of these accelerators in different processes of irradiation are exemplified. 相似文献
1000.