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231.
Armando Fernández Guillermet Per Gustafson Mats Hillert 《Journal of Physics and Chemistry of Solids》1985,46(12):1427-1429
It is sometimes advantageous to have an expression for the Gibbs energy, Gm(T,P), from which one can analytically derive an expression for the Heimholtz energy, Fm(T, Vm). Such an expression is suggested for solid substances and it is shown how expressions for other physical properties can be derived from it. 相似文献
232.
Gavin E. Crooks 《Journal of statistical physics》1998,90(5-6):1481-1487
An equality has recently been shown relating the free energy difference between two equilibrium ensembles of a system and an ensemble average of the work required to switch between these two configurations. In the present paper it is shown that this result can be derived under the assumption that the system's dynamics is Markovian and microscopically reversible. 相似文献
233.
234.
对理想气体或理想溶液有:■实际分析中有 X(大气)→1,■考虑评价的任一组分有 E_p=RT■,E_p 取决于 X■的选定和 X_p 环境监测值的大小,以此为基础进行环境质量评价方法探讨. 相似文献
235.
We propose a generalization of the Enskog equation for homogeneous dense systems including the complete three-particle dynamics. To this end the time derivative of the one-particle distribution is represented in the thermodynamic limit as the sum of three terms describing the effect of the initials-particle correlations, collisions withins-particle clusters, and coupling ofs-particle clusters to the surrounding gaseous medium, respectively. The analysis of casess=2 ands=3 is performed both for hard spheres and for a smooth, repulsive interaction. On assuming the equilibrium structure and spatial dependence of terms reflecting the effect of the medium, we obtain fors=2 the Enskog equation, and fors=3 a new equation, going beyond the Enskog theory. Apart from the Enskog collision term it contains additional contributions, and can be shown to reduce to the Choh-Uhlenbeck equation in the long-time, low-density limit. 相似文献
236.
A slight modification of the recent Penrose and Lebowitz treatment of thermodynamic metastable states is presented. For the case of periodic boundary conditions, this modification allows the condition of metastability to be extended to all the metastable states in the van der Waals-Maxwell theory of the liquid-vapor phase transition, that is, for all states satisfyingf
0()+1/2
2>f(, 0+) andf0()+x>0 wheref(, 0+) is the (stable) Helmholtz free energy density of the generalized van der Waals-Maxwell theory andf
0() is the Helmholtz free energy density of a reference system with no long-range interaction, is a mean field-type term arising from a long-range Kac interaction, is the overall mean particle density, andx is any positive number. For the case of rigid-wall boundary conditions, a more restrictive condition is placed onx. 相似文献
237.
Models having the thermodynamic properties of aqueous alkaline earth halides and NaCl-MgCl2 mixtures
Harold L. Friedman Anne Smitherman Raffaella De Santis 《Journal of solution chemistry》1973,2(1):59-81
A model studied earlier in relation to aqueous 1–1 electrolytes has been applied to the interpretation of the excess free energies of aqueous solutions of the alkaline earth halides up to 1 M ionic strength. Several variations on the model could be fitted to the data. In the one which seems most consistent with the other observations, the cospheres (hydration layers) on the M++ ions were two water molecules thick rather than one as for the alkali metal, tetraalkylammonium, and halide ions. The overlap of cospheres of an M++, M++ pair was found to make a small attractive contribution to the interionic force, while the overlap of cospheres of an M++, X– pair makes a small positive contribution which is almost the same for X–=Cl–, Br–, or I–. Thus, ionic hydration shells which are not penetrated by other ions are not required to account for the observed excess free energies. The model is also fitted to NaCl-MgCl2 mixtures to see whether the new cosphereoverlap parameter which must be determined is consistent with the others. The calculation also shows how the thermodynamic behavior of the mixtures is consistent with the mixture limiting law for unsymmetrical mixtures. The singularities in the mixing coefficients g0 and w0 at infinite dilution dominate their concentration dependence only up to ionic strengths of about 0.01 M in models which fit the data.Most of this report is abstracted from a thesis presented by A. Smitherman to the Graduate School of the State University of New York at Stony Brook in partial fulfillment of the requirements for the M.S. degree, August 1972. 相似文献
238.
Hans-J?rg Himmel 《Chemphyschem》2005,6(4):706-713
Quantum-chemical calculations were carried out to shed more light upon possible first intermediates formed during chemical vapour deposition (CVD) processes leading to III-V semiconductors. Information about possible structures of intermediates and about thermodynamic properties in dependence of the temperature were collected. Because some of the systems calculated herein contain a substantial number of atoms (up to 144), it is limited to intermediates on the way to solid AIN. According to our suggestion, the first intermediates are species with the overall formula AINH2, Al2N2H4, Al3N3H6, AI5N5H8, AI7N7H, and Al9N9H, AI12N12H12. In further calculations the growth of a second layer, on top of the first layer, which is modelled by the Al12N12H12 cluster, is simulated. The Al12N12H12 "surface" offers two places for the attachment of an Al3N3H6 ring. At temperatures of 1000 K, the deltaG value for this attachment is only slightly negative, which suggests that the molecules can move relatively freely on the surface. This might be of importance for a defect-free growth process. Up to four layers are built on top of the first Al12N12H12 layer leading to Al24N24H24 (two layers), Al36N36H36 (three layers) and Al48N48H48 (four layers). The structures are compared with that of solid AIN in its most stable Wurzit-type structure. 相似文献
239.
M. Sudersanan 《Journal of Chemical Sciences》1979,88(5):385-391
Synergism in the extraction of scandium by a mixture of di-2-ethylhexyl phosphoric acid and a β-diketone has been studied.
The nature of the extracted species has been investigated. The effect of temperature on extraction has been studied and synergism
has been explained on the basis of thermodynamic parameters of the extraction process. 相似文献
240.
利用基于密度泛函理论的第一性原理全势线性缀加平面波方法,研究了立方反ReO3结构Cu3N在零温(0K)零压下的平衡晶格常数、体弹模量及其对压强的一阶导数,计算结果与其他实验及理论结果基本相符.同时得出Cu3N的弹性常数,Poisson比等,并分析出Cu3N在零温零压下是稳定的.通过准谐Debye模型计算Cu3N的热力学性质,得到了Cu3N的晶格常数、等压比热容、等容比热容、热胀系数与温度和压强之间的关系,同时计算出不同温度不同压强下其体弹模量及Debye温度的值。 相似文献