全文获取类型
收费全文 | 119篇 |
免费 | 2篇 |
专业分类
化学 | 43篇 |
力学 | 8篇 |
数学 | 4篇 |
物理学 | 66篇 |
出版年
2021年 | 3篇 |
2020年 | 2篇 |
2016年 | 1篇 |
2015年 | 3篇 |
2013年 | 2篇 |
2012年 | 2篇 |
2011年 | 6篇 |
2010年 | 6篇 |
2009年 | 5篇 |
2008年 | 6篇 |
2007年 | 15篇 |
2006年 | 11篇 |
2005年 | 9篇 |
2004年 | 6篇 |
2003年 | 6篇 |
2002年 | 2篇 |
2001年 | 6篇 |
1999年 | 7篇 |
1998年 | 1篇 |
1995年 | 1篇 |
1994年 | 2篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1988年 | 1篇 |
1986年 | 3篇 |
1985年 | 3篇 |
1983年 | 1篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1973年 | 2篇 |
排序方式: 共有121条查询结果,搜索用时 15 毫秒
101.
102.
Brady C Callaghan PL Ciunik Z Coates CG Døssing A Hazell A McGarvey JJ Schenker S Toftlund H Trautwein AX Winkler H Wolny JA 《Inorganic chemistry》2004,43(14):4289-4299
The spin-crossover system [Fe(btpa)](PF(6))(2) (btpa = N,N,N',N'-tetrakis(2-pyridylmethyl)-6,6'-bis(aminomethyl)-2,2'-bipyridine) and the predominantly low-spin species [Fe(b(bdpa))](PF(6))(2) ((b(bdpa) = N,N'-bis(benzyl)-N,N'-bis(2-pyridylmethyl)-6,6'-bis(aminomethyl)-2,2'-bipyridine) have been characterized by means of X-ray diffraction. The unit cell of [Fe(btpa)](PF(6))(2) contains two crystallographically independent molecules revealing octahedral low-spin and quasi-seven-coordinated high-spin structures. The unit cell of [Fe(b(bdpa))](PF(6))(2) contains two crystallographically independent molecules one of which corresponds to a low-spin structure, while the other reveals a disordering. On the basis of magnetic susceptibility and M?ssbauer measurements, it has been proposed that this disorder involves low-spin and high-spin six-coordinated molecules. The structures of [Zn(btpa)](PF(6))(2) and [Ru(btpa)](PF(6))(2) have been determined also. Pulsed laser photoperturbation, coupled here with time-resolved resonance Raman spectroscopy (TR(3)), has been used to investigate, for the first time by this technique, the relaxation dynamics in solution on nanosecond and picosecond time scales of low-spin, LS ((1)A) --> high-spin, HS ((5)T) electronic spin-state crossover in these Fe(II) complexes. For the nanosecond experiments, use of a probe wavelength at 321 nm, falling within the pi-pi transition of the polypyridyl backbone of the ligands, enabled the investigation of vibrational modes of both LS and HS isomers, through coupling to spin-state-dependent angle changes of the backbone. Supplementary investigations of the spin-crossover (SCO) equilibrium in homogeneous solution and in colloidal media assisted the assignment of prominent features in the Raman spectra of the LS and HS isomers. The relaxation data from the nanosecond studies confirm and extend earlier spectrophotometric findings, (Schenker, S.; Stein, P. C.; Wolny, J. A.; Brady, C.; McGarvey, J. J.; Toftlund, H.; Hauser, A. Inorg. Chem. 2001, 40, 134), pointing to biphasic spin-state relaxation in the case of [Fe(btpa)](PF(6))(2) but monophasic in the case of [Fe(b(bdpa))](PF(6))(2). The picosecond results suggest an early process complete in 20 ps or less, which is common to both complexes and possibly includes vibrational relaxation in the initially formed (5)T(2) state. 相似文献
103.
The natural buoyancy of gas bubbles has hampered conventional electrokinetic methods of evaluating charge at the gas-liquid interface. In this study, bubbles are held by centripetal force at the centre of a horizontal, rotating cylinder filled completely with liquid. Migration of the bubble along the axis of the cylinder can be achieved by applying a gravity force or an electrophoretic force. An expression for the drag coefficient has been developed and used to calculate surface charge densities and electrokinetic potentials. In the presence of potassium chloride, anionic and non-ionic surfactants, the electrokinetic potentials were negative (~2–5 mV) at the air-aqueous interface. A cationic surfactant rendered the zeta potential positive. A knowledge of the air-aqueous interfacial rheology is desirable if the drag coefficient, and consequently the zeta potential, at all types of gas-liquid interfaces is to be evaluated. 相似文献
104.
Nuclear orientation measurements are used to determine the hyperfine hamiltonian for82Br implanted into Fe single crystals (dose 5×1014/cm–2 implant energy 80 keV). Using a model based upon channeling measurements a good fit to the temperature-dependent gamma anisotropy is obtained for a pure magnetic interaction experienced by the 36±5% of Br which implants substitutionally of magnitudeB
hf (substitutional)=840±120 kG, withB
hf (non-substitutional)<150 kG. This hamiltonian is used to deduce unknown multipole mixing ratios in the daughter82Kr decay. Hyperfine field systematics are shown to indicate a substitutionalFeBr field of 1000 kG, and the origins of this field and the smaller interstitial interaction are discussed. 相似文献
105.
106.
Donna C. Arnold John M. OCallaghan Aoife Sexton Joseph M. Tobin Heinz Amenitsch Justin D. Holmes Michael A. Morris 《Applied Surface Science》2009,255(23):9333-9342
If mesoporous thin films (MTFs) are to be utilised in device applications it is important that we produce films which not only possess a single pore direction across large substrate areas (in the range of microns) but are also relatively defect free. In this paper we report the use of confining architectures in the form of topographically patterned rectangular section channels etched into native silicon substrates to promote ordering of the mesopores. We discuss the effects of the channels on films with different thicknesses. The film thickness is shown to be a critical parameter in defining highly orientated and defect-free films and the data demonstrate that it is possible to achieve a single mesoporous silica domain across macroscopic dimensions with thin film thicknesses of approximately 200 nm but that critically pore order can be lost in ultra thin and thicker films produced by these methods. 相似文献
107.
Soft colloidal interactions in colloidal glasses are modeled using suspensions of multiarm star polymers. Using a preshearing protocol that ensures a reproducible initial state ("rejuvenation" of the system), we report here the evolution of the flow curve from monotonically increasing to one dominated by a stress plateau, demonstrating a corresponding shear-banded state. Phenomenological understanding is provided through a scalar model that describes the free-energy landscape. 相似文献
108.
109.
Godard C Callaghan P Cunningham JL Duckett SB Lohman JA Perutz RN 《Chemical communications (Cambridge, England)》2002,(23):2836-2837
Low temperature in-situ UV irradiation of toluene solutions containing bis(alkene)rhodium complexes and parahydrogen in conjunction with NMR monitoring enables the characterisation of unstable eta 2-solvent complexes and dihydrogen activation products. 相似文献
110.
Wassenius H Callaghan PT 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2004,169(2):5998-256
The resolution of NMR velocimetry is inherently limited by random displacements due to molecular self-diffusion, and has so far not extended below a few tens of microns. We report here an extension to the nanoscale domain, a result achieved by the use of slowly diffusing, NMR-visible core-shell latex particles. These particles comprise an oil core surrounded by a solid polymer shell, making spheres of diameter 370 nm. Using these particles in the annulus of a concentric cylinder Couette cell, we have measured flow-induced displacements down to a few hundreds of nanometers, allowing the observation of the solid-to-liquid transition of a glassy system. We envisage new possibilities for NMR velocimetry as an experimental tool for colloidal chemistry and physics. 相似文献