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1.
During the course of our investigation of the electron transfer properties of some redox species through highly hydrophobic
long chain alkanethiol molecules on gold in aqueous and non-aqueous solvents, we obtained some intriguing results such as
unusually low interfacial capacitance, very high values of impedance and film resistance, all of which pointed to the possible
existence of a nanometer size interfacial gap between the hydrophobic monolayer and aqueous electrolyte. We explain this phenomenon
by a model for the alkanethiol monolayer—aqueous electrolyte interface, in which the extremely hydrophobic alkanethiol film
repels water molecules adjacent to it and in the process creates a shield between the monolayer film and water. This effectively
increases the overall thickness of the dielectric layer that is manifested as an abnormally low value of interfacial capacitance.
This behaviour is very much akin to the ‘drying transition’ proposed by Lum, Chandler and Weeks in their theory of length
scale dependent hydrophobicity. For small hydrophobic units consisting of apolar solutes, the water molecules can reorganize
around them without sacrificing their hydrogen bonds. Since for an extended hydrophobic unit, the existence of hydrogen bonded
water structure close to it is geometrically unfavourable, there is a net depletion of water molecules in the vicinity leading
to the possible creation of a hydrophobic interfacial gap. 相似文献
2.
The cocrystal of 1,2-bis(diphenylphosphinoyl)ethane (DPPEO) with phenol (1:1) were studied theoretically with AM1, PM3, MNDO and MINDO/3 semi-empirical methods to elucidate its structure. The bond lengths and angles from theoretical studies of molecule DPPEO/phenol (1:1) were found to be as expected. Theoretical results, concerning with intermolecular van der Waals forces in cocrystal, were compared with the previously obtained experimental data and AM1 results were found to be the best fit for bond lengths and angles of DPPEO/phenol. 相似文献
3.
B. V. Derjaguin 《Progress in Surface Science》1992,40(1-4):240-251
A review is presented about research on surface forces and surface interactions conducted over the past half-century, with some emphasis on the pioneering contributions of the Department of Surface Phenomena at the Institute of Physical Chemistry of the USSR Academy of Sciences. 相似文献
4.
A. A. Afanas'ev V. M. Katarkevich A. N. Rubinov T. Sh. Éfendiev 《Journal of Applied Spectroscopy》2002,69(5):782-787
Spatial redistribution of microparticles in a suspension on exposure to the interference laser field depending on the parameters of the particles and the field characteristics has been analyzed theoretically. Results of experimental investigations are presented that illustrate the capture of an ensemble of polymeric small spheres and also of the lymphocytes of human blood and other microparticles in a liquid in the interference radiation bands of the He–Ne laser. 相似文献
5.
V. N. Starovoitov 《Mathematical Notes》1997,62(2):244-254
In the present paper we study the qualitative behavior ast→∞ of the solution of the Cauchy problem for a system of equations describing a dynamics of a two-component viscous fluid.
The model under consideration takes into account the mutual diffusion of the fluid components as well as their capillary interaction.
We describe the ω-limit set of trajectories of the dynamical system generated by the problem. It is proved that the stationary
solution of the problem, is a homogeneous stationary distribution of one of the components, is asymptotically stable. Any
other stationary solution is not asymptotically stable and is even unstable if there are no close stationary solutions corresponding
to a smaller energy level.
Translated fromMatematicheskie Zametki, Vol. 62, No. 2, pp. 293–305, August, 1997.
Translated by A. M. Chebotarev 相似文献
6.
Y.K. Gambhir J.P. Maharana C.S. Warke 《The European Physical Journal A - Hadrons and Nuclei》1998,3(3):255-262
The existence of broken pseudo-spin symmetry in the Pb nucleus has been studied in the relativistic mean field approach using
realistic Lagrangian parameters. Its relationship to spin orbit splitting and the vanishingly small surface delta character
of the mean spin orbit potential are investigated. In the 208Pb nucleus the broken pseudo-spin doublets are found to exist above the neutron (proton) Fermi surfaces.
Received: 16 April 1998 / Revised version: 26 June 1998 相似文献
7.
Stefanie M. Walz Thomas E. Malner Ulrich Mueller Rolf Muelhaupt 《Journal of Polymer Science.Polymer Physics》2003,41(4):360-367
We explored phase separation and self‐assembly of perfluoroalkyl segments at the surface of polymer films obtained from latices of semifluorinated acrylate copolymers and the corresponding latex blends of nonfluorinated and semifluorinated polyacrylates. With laser‐induced secondary mass spectrometry the fluorine distribution was measured after annealing above the minimum film‐forming temperature of the polymers up to a depth of several micrometers. Depth profiles of a semifluorinated acrylate homopolymer and latex blends thereof with fluorine‐free alkylacrylates with 25, 50, and 75 mol % semifluorinated acrylate as well as a copolymer comprised of alkyl acrylate and semifluorinated acrylate (50/50 mol %) were investigated. In the case of latex blends containing both semifluorinated polyacrylates and fluorine‐free or low‐fluorine polymers, self‐assembly accounted for enrichment of the perfluoroalkyl segments at the surface. Coatings exhibiting low surface energy and having a substantially reduced total fluorine content were obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 360–367, 2003 相似文献
8.
The solubilities of o-, m- and p-xylene in water were measured at 25.0°C up to 250, 385, and 50 MPa, respectively. The solubility increased with increasing pressure up to 120 MPa (50 MPa for p-xylene) and then decreased. The reaction volumes, Vo accompanying the dissolution at 0.1 MPa were estimated as –3.6±0.5, –3.4±0.5, and –4.1±0.5 cm3-mol–1 for o-, m-, and p-xylene, respectively, from the pressure dependences of the solubilities. The limiting partial molar volumes, of p- and o-xylene in water under high pressure were estimated from Vo and the molar volume of the xylene. The partial molar volumes decreased with increasing pressure. The reaction volume for the formation of intra-molecular pairwise hydrophobic interaction between the methyl groups, as proposed by Ben-Naim, is discussed for the Vo of p- and o-xylene at 0.1 MPa. 相似文献
9.
Summary The complete error potential is used for the study of the correlation of molecules. The correlation can be seen as a relaxation of the electrons and a relaxation of the nuclei. From the Fermi sea, the electronic relaxation gives rise to a partial excitation of each orbital which collectively generates a linear, a surface or a volume pressure; the resulting forces acting on the nuclei are defined in a general theory of the intramolecular forces. H3, H
3
+
, the diatoms and the hydrid of the first nine elements are taken as examples. 相似文献
10.