全文获取类型
收费全文 | 507篇 |
免费 | 23篇 |
国内免费 | 2篇 |
专业分类
化学 | 346篇 |
晶体学 | 1篇 |
力学 | 52篇 |
数学 | 52篇 |
物理学 | 81篇 |
出版年
2022年 | 4篇 |
2021年 | 9篇 |
2020年 | 9篇 |
2019年 | 3篇 |
2018年 | 4篇 |
2016年 | 16篇 |
2015年 | 16篇 |
2014年 | 12篇 |
2013年 | 22篇 |
2012年 | 32篇 |
2011年 | 28篇 |
2010年 | 19篇 |
2009年 | 8篇 |
2008年 | 29篇 |
2007年 | 25篇 |
2006年 | 20篇 |
2005年 | 22篇 |
2004年 | 27篇 |
2003年 | 12篇 |
2002年 | 13篇 |
2001年 | 9篇 |
2000年 | 11篇 |
1999年 | 7篇 |
1998年 | 11篇 |
1996年 | 7篇 |
1995年 | 6篇 |
1994年 | 10篇 |
1993年 | 9篇 |
1992年 | 5篇 |
1991年 | 5篇 |
1990年 | 9篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1987年 | 6篇 |
1986年 | 7篇 |
1985年 | 11篇 |
1984年 | 3篇 |
1983年 | 5篇 |
1982年 | 5篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 8篇 |
1978年 | 4篇 |
1977年 | 7篇 |
1976年 | 3篇 |
1973年 | 4篇 |
1972年 | 3篇 |
1969年 | 3篇 |
1968年 | 3篇 |
1960年 | 3篇 |
排序方式: 共有532条查询结果,搜索用时 15 毫秒
21.
Levason W Matthews ML Reid G Webster M 《Dalton transactions (Cambridge, England : 2003)》2004,(1):51-58
High yield syntheses for 1,2-, 1,3-, and 1,4-xylyl distibines (1,2-C6H4(CH2SbMe2)2, 1,3-C6H4(CH2SbMe2)2, 1,4-C6H4(CH2SbMe2)2, respectively) from Me2SbCl (conveniently made in situ from Me2PhSb and HClgas) and the appropriate di-Grignard are reported. The 1,3- and 1,4-phenylene distibines, 1,3-C6H4(SbMe2)2 and 1,4-C6H4(SbMe2)2, were made similarly. The new ligands have been characterised by mass spectrometry, 1H and 13C[1H] NMR spectroscopy, and by the preparation of methiodide derivatives. The crystal structures of 1,4-C6H4(CH2SbMe2)2 and [1,3-C6H4(CH2SbMe3)2]I2 have been determined. The synthesis of 1,2-C6H4(CH2SbPh2)2 has been achieved similarly in modest yield and the distibine converted into the tetra-iodo-derivative 1,2-C6H4(CH2SbPh2I2)2. The coordination modes available to these ligands have been probed by the synthesis and characterisation of complexes with nickel, iron and tungsten carbonyls. The crystal structure of [[Fe(CO)4]2[micro-1,3-C6H4(CH2SbMe2)2]] has been determined. The spectroscopic properties of these carbonyl derivatives have been compared with those of complexes of other antimony ligands, and in some cases with diphosphine and diarsine complexes, to probe the electronic properties of the new ligands. 相似文献
22.
Some dimer models are proposed for the hydrated and ammoniated electron. These combine features of both the cavity and polaron formulations. By way of an extended Hückel calculation the size of the cavities in water and ammonia is ascertained. A population analysis shows that whereas in water the charge spreads out almost uniformly over the system, in ammonia the electron remains within the cavity.
Zusammenfassung Einige dimere Modelle, die Züge der Loch- und Polaronenvorstellungen vereinigen, werden für das hydratisierte und ammonisierte Elektron vorgeschlagen. Mit Hilfe der erweiterten Hückel-Theorie wird die Grö\e der Löcher in Wasser und Ammoniak bestimmt. Dabei zeigt sich, da\ die Ladung im Wasser fast gleichmÄ\ig über das System verteilt ist, wÄhrend im Ammoniak das Elektron innerhalb des Loches bleibt.
Résumé On propose des modèles de dimères pour l'électron hydraté et ammoniaqué. Ces modèles combinent les caractéristiques des formulations de cavité et de polaron. A l'aide d'un calcul Hückel étendu, on fixe la taille des cavités dans l'eau et l'ammoniaque. L'analyse de population montre que dans l'ammoniaque l'électron reste dans la cavité, tandis que dans l'eau la charge s'étend presque uniformément sur le système.相似文献
23.
A. Bergier H. Gennow S. Nilsson J. Norrby W. Evans J. R. Fry P. Mason H. Muirhead H. Fenker J. Marraffino S. Reucroft C. Roos M. S. Webster 《Zeitschrift fur Physik C Particles and Fields》1980,5(4):265-274
We present data on \(\bar pn\) and π? n collisions obtained from an exposure of the 30′' FNAL deuterium filled bubble chamber to a mixed \({{\bar p} \mathord{\left/ {\vphantom {{\bar p} {\pi ^ - }}} \right. \kern-0em} {\pi ^ - }}\) beam with a momentum of 100 GeV/c. We find that in 17±2% of the collisions with the antiproton there is an interaction on the spectator while for the collisions with π? mesons the corresponding number is 15±2%. The \(\bar pn\) and π? n multiplicity distributions have average charged multiplicities of 6.46±0.07 and 6.53±0.08 respectively. The average multiplicities for both types of interactions are slightly smaller than those for the corresponding reactions on hydrogen by an amount that is the same as observed at other energies. As an estimate of \(\bar pn\) annihilation we have calculated the difference \(\sigma _n (\bar pn) - \sigma _n (pn)\) for each prong numbern. We find an average multiplicity of 9±1, a value close to that for \(\bar pp\) annihilation at the same energy. combining our data with lower energy \(\bar pn\) annihilation data, we observe that the average negative multiplicity is systematically larger than that for \(\bar pp\) annihilation similar to the difference between neutron and proton target data with other beam projectiles. 相似文献
24.
Kim K Webster S Levi N Carroll DL Pinto MR Schanze KS 《Langmuir : the ACS journal of surfaces and colloids》2005,21(11):5207-5211
We describe the preparation and characterization of a photonic crystal filled with a luminescent conjugated polyelectrolyte, sulfonated poly(phenylene ethynylene). The conjugated polymer was coated onto the nanospheres by the layer-by-layer method and assembled directly into a fluorescent opal structure avoiding the defects associated with post-filling schemes. These structures exhibit strong angle-dependent luminescent properties. By using multiple layers, we further demonstrate control over the emissive bands of the opal. 相似文献
25.
The rubidium contents of a granite (G-1), a diabase (W-1) and sea-water have been determined by mass spectrometric isotope dilution analysis. The values found are: G-1, 214 p.p.m-; W-1, 21.3 p.p.m.; sea water, 121.4 μg/l. These results show excellent agreement with values obtained at Harwell by neutron activation analysis, and the coefficient of variation for four determinations is usually ±1–2%.Rubidium ions were produced in the mass spectrometer by either a side filament or a centre filament technique. The former method enables rubidium and lithium determinations to be combined; the results obtained by the second method suggest that concentrations of the order of 1 p.p.m. may be determined for a sample of only a few mg with little chemical treatment beyond that required to decompose the sample. 相似文献
26.
Levason W Matthews ML Reid G Webster M 《Dalton transactions (Cambridge, England : 2003)》2004,(4):554-561
Complexes of the title ligand with Cu(I), Ag(I), Au(I), Pd(II), Pt(II), Rh(III), and rare examples with Ni(II) and Co(III) have been prepared and characterised by analysis, IR, UV-vis, 1H, 63Cu and 59Co NMR spectroscopy and ES+ mass spectrometry as appropriate. The structures of [Cu[1,2-C6H4(CH2SbMe2)2]2]BF4, [PtCl2[1,2-C6H4(CH2SbMe2)2]], [M[1,2-C6H4(CH2SbMe2)2]2][PF6]2 (M = Pd or Pt), and [NiI[1,2-C6H4(CH2SbMe2)2]2]ClO4 have been determined, and the varying chelate bite and conformations of the xylyl backbone in these structures are discussed. Despite the unfavourable seven-membered chelate ring and the large soft antimony donors, 1,2-C6H4(CH2SbMe2)2 proves to be a surprisingly good ligand for late transition metals in medium oxidation states. 相似文献
27.
Adams RD Miao S Smith MD Farach H Webster CE Manson J Hall MB 《Inorganic chemistry》2004,43(8):2515-2525
The reaction of Mn(2)(CO)(7)(mu-S(2)) with [CpNi(CO)](2) yielded the paramagnetic new compound Cp(2)Ni(2)Mn(CO)(3)(mu(3)-S)(2) (1) and a new hexanuclear metal product Cp(2)Ni(2)Mn(4)(CO)(14)(mu(6)-S(2))(mu(3)-S)(2) (2). Structurally, compound 1 contains two triply bridging sulfido ligands on opposite sides of an open Ni(2)Mn triangular cluster. EPR and temperature-dependent magnetic susceptibility measurements of 1 show that it contains one unpaired electron. The electronic structure of 1 was determined by Fenske-Hall molecular orbital calculations which show that the unpaired electron occupies a low lying antibonding orbital delocalized unequally across the three metal atoms. The selenium homologue Cp(2)Ni(2)Mn(CO)(3)(mu(3)-Se)(2) (3) was obtained from the reaction of a mixture of Mn(2)(CO)(10) and [CpNi(CO)](2) with elemental selenium and Me(3)NO.2H(2)O. It also has one unpaired electron. Compound 1 reacted with elemental sulfur to yield the dinickeldimanganese compound, Cp(2)Ni(2)Mn(2)(CO)(6)(mu(4)-S(2))(mu(4)-S(5)), 4, which can also be made from the reaction of Mn(2)(CO)(7)(mu-S(2)) with [CpNi(CO)](2) and sulfur. Compound 4 was converted back to 1 by sulfur abstraction using PPh(3). The reaction of Mn(2)(CO)(10) with [CpNi(CO)](2) in the presence of thiirane yielded the ethanedithiolato compound CpNiMn(CO)(3)(mu-SCH(2)CH(2)S) (5), which was also obtained from the reaction of Mn(4)(CO)(15)(mu(3)-S(2))(mu(4)-S(2)) with [CpNi(CO)](2) in the presence of thiirane. Compound 5 reacted with additional quantities of thiirane to yield the new compound CpNiMn(CO)(3)[mu-S(CH(2)CH(2)S)(2)], 6, which contains a 3-thiapentanedithiolato ligand that bridges the two metal atoms. Compound 6 was also obtained from the reaction of Mn(2)(CO)(10) with [CpNi(CO)](2) and thiirane. The molecular structures of the new compounds 1-6 were established by single-crystal X-ray diffraction analyses. 相似文献
28.
Capillary GC coupled to an atomic emission detector (AED) provides a powerful new hyphenated technique for the separation and characterization of complex mixtures and compounds. The AED provides simultaneous and truly specific multi-element detection. The specificity of detection reduces the need for the complex sample pretreatment procedures which are necessary to reduce the interference from co-eluted substances which is experienced with detectors such as the FID and the ECD. A range of environmentally significant problems has been studied, including PCB analysis, the characterization of the reaction products of a novel waste treatment process, and the profiling of sulfur-containing species formed by the pyrolysis of various types of coal. 相似文献
29.
Edith Chow Burkhard Raguse Karl‐H. Müller Lech Wieczorek Avi Bendavid James S. Cooper Lee J. Hubble Melissa S. Webster 《Electroanalysis》2013,25(10):2313-2320
The porosity of 1‐hexanethiol‐functionalised gold nanoparticle films was assessed and utilised as chemiresistor sensors. Electrochemical capacitance measurements showed that the accessibility of electrolytes of different ionic strengths into the pores depended on the thickness of the electric double layer formed. A large variation in capacitance was measured in 0.01–1000 mM NaClO4, implying a wide pore size distribution. The change in morphology of the nanoparticle films upon storage in air, water and ethanol for two weeks was investigated. There was a significant decrease in the electrochemical capacitance at high electrolyte concentrations for the ethanol‐stored films compared to the freshly‐prepared films suggesting a decrease in the number of small pores of radii in the range of 0.3–3 nm. This was further supported by optical topographical measurements where a decrease in the thickness of ethanol‐stored films was observed relative to the freshly‐prepared films. The porous nature of the nanoparticle films was found to have an effect on the chemical sensing behaviour. When used as chemiresistor sensors, for the detection of heptane in water, the ethanol‐stored films provided larger resistance changes and longer response times. This suggests that the more densely packed ethanol‐stored films provided more sites that enabled film swelling, and that diffusion of the analyte occurred through the narrower water‐filled pores. This demonstrates the effect of different storage conditions on film morphology and subsequently sensor response. 相似文献
30.
Ronald Webster 《国际流体数值方法杂志》2013,71(4):488-505
An investigation is made of the performance of algebraic multigrid (AMG) solvers for the discrete Stokes problem. The saddle‐point formulations are based on the direct enforcement of the fundamental conservation laws in discrete spaces and subsequently stabilised with the aid of a regular splitting of the diffusion operator. AMG solvers based on an independent coarsening of the fields (the unknown approach) and also on a common coarsening (the point approach) are investigated. Both mixed‐order and equal‐order interpolations are considered. The dependence of convergence on the ‘degree of coarsening’ is investigated by studying the ‘convergence versus coarsening’ characteristics and their variation with mesh resolution. They show a consistency in shape, which reveals two distinct performance zones, one convergent the other divergent. The transition from the convergent to the divergent zones is discontinuous and occurs at a critical coarsening factor that is largely mesh independent. It signals a breakdown in the stability of the smoothing at the coarser levels of coarse grid approximation. It is shown that the previously observed, mesh‐dependent, scaling of convergence factors, which had suggested inconsistencies in the coarse grid approximation, is not a reliable marker of inconsistency. It is an indirect consequence of the breakdown in the stability of smoothing. For stable smoothing, reduction factors are shown to be largely mesh independent. The ability of mixed‐order interpolation to permit stable smoothing and therefore to deliver mesh‐independent convergence is explained. Two expedient options are suggested for obtaining mesh‐independent convergence for those AMG codes that are based on an equal‐order interpolation. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献