首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   74119篇
  免费   5993篇
  国内免费   7665篇
化学   30131篇
晶体学   682篇
力学   6606篇
综合类   1252篇
数学   25010篇
物理学   24096篇
  2023年   659篇
  2022年   1261篇
  2021年   1414篇
  2020年   1528篇
  2019年   1798篇
  2018年   1479篇
  2017年   1767篇
  2016年   1991篇
  2015年   1818篇
  2014年   2582篇
  2013年   4785篇
  2012年   3122篇
  2011年   3530篇
  2010年   2995篇
  2009年   4156篇
  2008年   4505篇
  2007年   4801篇
  2006年   4473篇
  2005年   3770篇
  2004年   3456篇
  2003年   3458篇
  2002年   3165篇
  2001年   2687篇
  2000年   2610篇
  1999年   2341篇
  1998年   2173篇
  1997年   1794篇
  1996年   1612篇
  1995年   1442篇
  1994年   1325篇
  1993年   1129篇
  1992年   1113篇
  1991年   847篇
  1990年   701篇
  1989年   606篇
  1988年   555篇
  1987年   436篇
  1986年   371篇
  1985年   436篇
  1984年   426篇
  1983年   208篇
  1982年   344篇
  1981年   403篇
  1980年   301篇
  1979年   293篇
  1978年   220篇
  1977年   206篇
  1976年   154篇
  1974年   109篇
  1973年   110篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
81.
The intermolecular interaction energy for reacting systems in singlet, triplet and doublet states was partitioned by the perturbation expansion method into the chemically meaningful five interaction terms: the Coulomb, exchange-repulsion, induction, dispersion, and charge-transfer energies. In the local ZDO approximation, these energy terms were evaluated for the dimerization of methylenes (1,3CH2), the additions of carbenes (1,3CH2 and1,3CF2) as well as amino radicals (2NH2 and2NF2) toward ethylene, and the hydrogen abstractions by methylenes (1,3CH2), nitrene (3NH), and hydroxyl radical (2OH) from methane. It has been found that the reaction path is much influenced by the spinmultiplicity, and that the charge-transfer and exchange-repulsion terms play a dominant role in determining the course of reactions.  相似文献   
82.
83.
The synthesis of bulk Y2Ba4Cu7O15-δ superconductor at atmospheric oxygen pressure via solid state sintering is reported. Temperature ranging from 860 to 890 °C as well as time interval over 2 to 15 days were used to investigate the formation of the Y2Ba4Cu7O15-δ phase. A time-temperature profile characterizing the conditions for the preparation of Y2Ba4Cu7O15-δ phase suggests the optimal condition to be sintering at 890 °C for over 10 days. Detailed results of X-ray diffraction, electrical resistivity, iodometric titration and magnetization measurements are described.  相似文献   
84.
The crystal structure of a second high-pressure copper vanadate phase, CuVO3(II), has been determined and refined by full-matrix least-squares procedures using automatic diffractometer data to a residual R = 0.042 (Rw = 0.051). The space group is rhombohedral, R3, with hexagonal unit cell a = 4.966(2) and c = 14.084(5) Å [aR = 5.501(2) Å and α = 53.66(3)°]. The structure is the fully ordered ilmenite-type and, on the basis of published magnetic data and the interatomic distances, the valence distribution Cu+V5+O3 is proposed. This represents a unique example of Cu+ in an octahedral environment.  相似文献   
85.
Characteristic features of reactions involving esters of phosphorus-containing acids in highly organized media (micelles, liquid crystals, vesicles, and emulsions) are surveyed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 298–312, February, 1996.  相似文献   
86.
The parallel between orbital first and second electric moments and statistical first and second central moments is noted. Three measures of orbital spatial distribution in terms of their moments are proposed, and applied to the LMO's in a series of ten-electron hydrides. Consistent differences between bond and lone pair distributions are found. Using the statistical interpretation, for each LMO an effective solid angle around the central atom is postulated.  相似文献   
87.
In distinction to Extended Hückel Theory which predicts as the most stable conformation of free zwitterionic GABA a totally extended form, PCILO and SCF ab initio studies show that the intrinsically preferred conformation of the isolated molecule is a highly folded one, resulting from strong interactions between the two charged ends. Computations are also carried out for hydrated GABA in the supermolecule approach allowing moreover for the flexibility of binding of some of the water molecules of the first hydration shell. They predict the coexistence in solution of a large number of conformations showing different degrees of folding (or extension), a result confirmed by recent NMR studies. This and a number of similar results show that we have to adapt our thinking on the role of conformations in pharmacological activity to this situation, which was frequently obscured by the more abundant results of X-ray crystallography yielding a single conformation.  相似文献   
88.
The apparent molal volumes and compressibilities of NaCl, KCl, and CsCl in mixtures of 18-Crown-6 and water have been calculated from density and speed-of-sound measurements at 25°C. The partial molal volumes and compressibilities of the salts when all cations have formed complexes with 18-Crown-6 molecules have been evaluated. The sign and magnitude of the volume and compressibility changes of complex formation strongly suggest that the charge of the cation becomes very effectively screened by the crown ether.  相似文献   
89.
Langlet  J.  Claverie  P.  Pullman  B.  Piazzola  D.  Daudey  J. P. 《Theoretical chemistry accounts》1977,46(2):105-116
The effect of water on the conformational preferences of acetylcholine has been studied within the discrete, the continuum and the combined discrete-continuum models described in parts I and II of this series. All the models lead to the conclusion that the trans-gauche form which is, following refined quantum-mechanical computations, the intrinsically preferred one and the one observed in the crystal of acetylcholine and of a number of analogues should remain also the preferred conformation in water. This result agrees with NMR studies. The results of the empirical discrete model used here compare favorably to those obtained by an ab initio super-molecule treatment. The continuum model utilized here represents a net improvement above such models utilized in other works.  相似文献   
90.
A non-empirical molecular orbital method, particularly suitable for calculations on cage-like molecules, is described. The method uses as basis functions the set of free-electron functions which are the solutions of Schrödinger's equation for an electron confined between two concentric, spherical potential energy barriers. Application of the theory to the SCF calculation of the energies of the delocalized electrons in benzene and tetrasulphur tetranitride shows that the model is capable of interpreting the properties of such systems. However, it does highlight a difficulty in the calculation of excited state energies with one-centre models which appears to be largely unrecognized.Extension of the method to a consideration of all the valence electrons, using P4 as an example, reveals problems the origin of which is an inadequate treatment of the core electrons. It is suggested that these problems may best be dealt with by use of a suitable pseudo potential.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号