全文获取类型
收费全文 | 5430篇 |
免费 | 236篇 |
国内免费 | 27篇 |
专业分类
化学 | 3869篇 |
晶体学 | 40篇 |
力学 | 155篇 |
综合类 | 2篇 |
数学 | 675篇 |
物理学 | 952篇 |
出版年
2023年 | 45篇 |
2022年 | 47篇 |
2021年 | 68篇 |
2020年 | 99篇 |
2019年 | 89篇 |
2018年 | 53篇 |
2017年 | 62篇 |
2016年 | 170篇 |
2015年 | 147篇 |
2014年 | 166篇 |
2013年 | 264篇 |
2012年 | 315篇 |
2011年 | 377篇 |
2010年 | 206篇 |
2009年 | 187篇 |
2008年 | 299篇 |
2007年 | 312篇 |
2006年 | 297篇 |
2005年 | 262篇 |
2004年 | 239篇 |
2003年 | 179篇 |
2002年 | 188篇 |
2001年 | 116篇 |
2000年 | 113篇 |
1999年 | 105篇 |
1998年 | 66篇 |
1997年 | 51篇 |
1996年 | 54篇 |
1995年 | 79篇 |
1994年 | 70篇 |
1993年 | 62篇 |
1992年 | 69篇 |
1991年 | 60篇 |
1990年 | 51篇 |
1989年 | 44篇 |
1988年 | 26篇 |
1987年 | 35篇 |
1985年 | 45篇 |
1984年 | 25篇 |
1983年 | 31篇 |
1982年 | 35篇 |
1981年 | 28篇 |
1980年 | 34篇 |
1979年 | 36篇 |
1978年 | 34篇 |
1977年 | 47篇 |
1976年 | 28篇 |
1975年 | 31篇 |
1974年 | 38篇 |
1973年 | 28篇 |
排序方式: 共有5693条查询结果,搜索用时 15 毫秒
71.
High nuclearity paramagnetic, spin-coupled transition metal clusters and grids are fascinating chemists and physicists partly because of their structural beauty, and the challenge of creating them, but also because of their novel physical properties. Magnetic interactions between the spin centers are a primary focus. This review will examine a selection of Mn(II) polynuclear grids and clusters, with nuclearities in the range Mn4 to Mn9. Theoretical treatments of the magnetic properties are discussed, and approaches to solving the exchange problem for ‘large’ spin systems related to computational difficulties. A freely available software package (MAGMUN4.1) is presented as a means of dealing simply with spin-coupled clusters in general, and symmetry reduction methods are discussed briefly as a means of dealing with ‘large’ spin systems. 相似文献
72.
Friggeri A Gronwald O van Bommel KJ Shinkai S Reinhoudt DN 《Journal of the American Chemical Society》2002,124(36):10754-10758
The synthesis of a new saccharide-based gelator (2) containing a donor moiety has been described. Gelation experiments of a dual-component gel consisting of a saccharide-based gelator bearing an acceptor group (1) and of 2 have been performed in a variety of organic solvents and water. Moreover, gelation tests at different molar ratios of 1 and 2 have been performed in water, octanol, and diphenyl ether. In these last two solvents a gel color change was observed, from colorless to yellow, upon cooling of the sample to room temperature. This phenomenon was further investigated by UV-visible spectroscopy, which revealed the presence of charge-transfer interactions in the gel, in octanol. Temperature-dependence UV spectroscopy confirmed that such interactions occur in the gel but not in the corresponding solution sample. Furthermore, T(gel) measurements show that dual-component gels of 1 and 2 present increased thermal stability at a 50:50 ratio of the two gelators, in dependence of the solvent. Transmission electron microscopy (TEM) images of the single-component gels in diphenyl ether revealed that they consist of a fibrous network, while the dual-component gel presents a novel, helical, fibrous-bundle structure. 相似文献
73.
Ahunbay MG Perez-Pellitero J Contreras-Camacho RO Teuler JM Ungerer P Mackie AD Lachet V 《The journal of physical chemistry. B》2005,109(7):2970-2976
In this third article of the series, a new anisotropic united atoms (AUA) intermolecular potential parameter set has been proposed for the carbon force centers connecting the aromatic rings of polyaromatic hydrocarbons to predict thermodynamic properties using both the Gibbs ensemble and NPT Monte Carlo simulations. The model uses the same parameters as previous AUA models used for the aromatic CH force centers. The optimization procedure is based on the minimization of a dimensionless error criterion incorporating various thermodynamic data of naphthalene at 400 and 550 K. The new model has been evaluated on a series of polyaromatic and naphthenoaromatic hydrocarbons over a wide range of temperatures up to near-critical conditions. Vaporization enthalpy, liquid density, and normal boiling temperature are reproduced with good accuracy. The new potential parameters have also been tested successfully on toluene, 1,3,5-trimethylbenzene, styrene, m-xylene, n-hexylbenzene, and n-dodecylbenzene to demonstrate their transferability to alkylbenzenes. 相似文献
74.
Feth MP Bolm C Hildebrand JP Köhler M Beckmann O Bauer M Ramamonjisoa R Bertagnolli H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(6):1348-1359
XANES and EXAFS spectroscopic studies at the Mn-K- and Br-K-edge of reaction products of (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) chloride ([(salen)Mn(III)Cl], 1) and (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) bromide ([(salen)Mn(III)Br], 2) with 4-phenylpyridine N-oxide (4-PPNO) and 3-chloroperoxybenzoic acid (MCPBA) are reported. The reaction of the Mn(III) complexes with two equivalents of 4-PPNO leads to a hexacoordinated compound, in which the manganese atom is octahedrally coordinated by four oxygen/nitrogen atoms of the salen ligand at an average distance of approximately 1.90 A and two additional, axially bonded oxygen atoms of the 4-PPNO at 2.25 A. The oxidation state of this complex was determined as approximately +IV by a comparative study of Mn(III) and Mn(V) reference compounds. The green intermediate obtained in reactions of MCPBA and solutions of 1 or 2 in acetonitrile was investigated with XANES, EXAFS, UV/Vis, and Raman spectroscopy, and an increase of the coordination number of the manganese atoms from 4 to 5 and the complete abstraction of the halide was observed. A formal oxidation state of IV was deduced from the relative position of the pre-edge 1s-->3d feature of the X-ray absorption spectrum of the complex. The broad UV/Vis band of this complex in acetonitrile with lambda(max)=648 nm was consistent with a radical cation structure, in which a MCPBA molecule was bound to the Mn(IV) central atom. An oxomanganese(V) or a dimeric manganese(IV) species was not detected. 相似文献
75.
Yencha AJ Lopes MC King GC Hochlaf M Song Y Ng CY 《Faraday discussions》2000,(115):355-62; discussion 407-29
The pulsed-field ionization (PFI) photoelectron (PE) spectrum of HF has been recorded at the chemical dynamics beamline of the advanced light source over the photon energy range 15.9-16.5 eV using a time-of-flight selection scheme at a resolution of 0.6 meV. Rotationally-resolved structure in the HF+(X 2 pi 3/2, 1/2, v+ = 0, 1) band systems are assigned. The spectral appearance of these systems agrees with a previous VUV laser PFI-PE study. Importantly, extensive rotationally-resolved structure between these two vibrational band systems is also observed. This is attributed to ion-pair formation via Rydberg states converging on the v+ = 1 vibrational levels of the HF+(X 2 pi 3/2, 1/2) spin-orbit states. These Rydberg states are assigned to the 1 sigma+ part of the nd-complexes (sigma, pi, and delta). Ion-pair formation is observed in this study by the detection of F- ions. Some partially rotationally-resolved structure in a previously published threshold photoelectron spectrum is similarly attributed to ion-pair formation (F- detection) through a combination of the v+ = 17 level of the (A 2 sigma+) 3s sigma Rydberg state and the (X 2 pi 3/2, 1/2, v+ = 1) 7d Rydberg states. On the basis of the present study, an accurate experimental value for the dissociation energy of the ground state of HF has been obtained, D0(HF) = 5.8650(5) eV. 相似文献
76.
King RB 《Inorganic chemistry》2005,44(3):466-467
The metallaborane Cp4Co4B4H4 and the organometallic cluster Cp4Fe4C4H4 (Cp = eta5-cyclopentadienyl) not only are isoelectronic but also exhibit completely analogous eight-vertex bisdisphenoidal structures. Such structures, as well as the tetracapped tetrahedral structure of the Cp4Fe4(mu3-CO)4 precursor to Cp4Fe4C4H4, can be derived from a cube by insertion of diagonals in each of the six faces. Furthermore, the formation of Cp4Fe4C4H4 from Cp4Fe4(mu3-CO)4 can be described as a double diamond-square-diamond process preserving D2d symmetry throughout the process. 相似文献
77.
Frank D. King 《Tetrahedron》2007,63(9):2053-2056
A high yielding cyclisation of the readily available N-(4,4-diethoxybutyl)-2-(3,4-dimethoxyphenyl)acetamide to 8,9-bis(methyloxy)-2,3,6,10b-tetrahydropyrrolo[2,1-a]isoquinolin-5(1H)-one is described. The latter can be reduced with either AlH3 or BH3 to (±)-crispine A in an overall yield of 55%. 相似文献
78.
79.
[reaction: see text] Glucuronyl iodide 1 has been studied in detail as a "disarmed" glycosyl donor. In a model reaction, using N-iodosuccinimide (NIS) as a promoter and 2-phenylethanol as acceptor, best results were obtained using NIS with I(2), followed by trimethylsilyltrifluoromethanesulfonate (TMSOTf). When a series of primary and secondary alcohols was glycosylated using these conditions, yields of 60-83% of beta-glucuronides were obtained. Various "nonheavy" metal salts also effectively catalyzed the model reaction but led to significant amounts of alpha-product with less reactive secondary alcohols. 相似文献
80.
Absorption transitions to vibrational levels close to the A state dissociation limit of ICI have been examined using a two-photon sequential absorption technique. The discrete rotational structures of I37 Cl bands to within 0.7 cm?1 of the limit have been selectively excited and analysed. A value of 17557.514 ± 0.030 cm?1 has been obtained for the I(2Po) + Cl(2Po) dissociation energy De, relative to the minimum of the ICI ground state potential well. The two-photon technique can be used to excite and display separately the high resolution absorption spectra of different isotopic species of a molecule which are contained in a mixture. 相似文献