全文获取类型
收费全文 | 5096篇 |
免费 | 138篇 |
国内免费 | 14篇 |
专业分类
化学 | 3625篇 |
晶体学 | 20篇 |
力学 | 75篇 |
数学 | 694篇 |
物理学 | 834篇 |
出版年
2021年 | 42篇 |
2020年 | 39篇 |
2019年 | 41篇 |
2018年 | 32篇 |
2016年 | 80篇 |
2015年 | 95篇 |
2014年 | 100篇 |
2013年 | 205篇 |
2012年 | 148篇 |
2011年 | 164篇 |
2010年 | 121篇 |
2009年 | 105篇 |
2008年 | 144篇 |
2007年 | 164篇 |
2006年 | 179篇 |
2005年 | 175篇 |
2004年 | 173篇 |
2003年 | 144篇 |
2002年 | 145篇 |
2001年 | 112篇 |
2000年 | 85篇 |
1999年 | 77篇 |
1998年 | 84篇 |
1997年 | 71篇 |
1996年 | 103篇 |
1995年 | 85篇 |
1994年 | 85篇 |
1993年 | 84篇 |
1992年 | 91篇 |
1991年 | 92篇 |
1990年 | 73篇 |
1989年 | 108篇 |
1988年 | 81篇 |
1987年 | 97篇 |
1986年 | 86篇 |
1985年 | 111篇 |
1984年 | 126篇 |
1983年 | 72篇 |
1982年 | 110篇 |
1981年 | 93篇 |
1980年 | 83篇 |
1979年 | 109篇 |
1978年 | 77篇 |
1977年 | 84篇 |
1976年 | 80篇 |
1975年 | 63篇 |
1974年 | 100篇 |
1973年 | 58篇 |
1972年 | 29篇 |
1971年 | 43篇 |
排序方式: 共有5248条查询结果,搜索用时 312 毫秒
61.
F. Gutbrod G. Kramer G. Rudolph G. Schierholz 《Zeitschrift fur Physik C Particles and Fields》1987,35(4):543-549
TheO(α s 2 ) QCD corrections to the thrust distribution for three-jet production ine + e ? annihilation are found to depend on the algorithm for recombining four partons into three jets. Several recombination schemes are discussed and results are compared. Results of the recombination approach are compared also to recent direct calculations of three-jet thrust distributions. The importance of terms proportional to jet resolution parameters is stressed. 相似文献
62.
Minko S Müller M Motornov M Nitschke M Grundke K Stamm M 《Journal of the American Chemical Society》2003,125(13):3896-3900
We report a route to fabricate two-level structured self-adaptive surfaces (SAS) of polymer materials. The first level of structure is built by a rough polymer film that consists of needlelike structures of micrometer size. The second level of structure is formed by the nanoscopic self-assembled domains of a demixed polymer brush irreversibly grafted onto the needles. By exposing the surface to solvents that are selective to one of the components of the brush, we reversibly tune the surface properties. The large-scale surface structure amplifies the response and enables us to control wettability, adhesion, and chemical composition of the surface over a wide range. 相似文献
63.
T. Dresch H. Kramer Y. Thurner R. Weber 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1991,18(4):391-397
Photodissociation of negatively charged sulfur dioxide clusters (SO2) n ? , 2≦n≦11, was investigated in the wavelength range between 458 nm and 600 nm using a tandem mass spectrometer. The spectral position of the absorption band remains unchanged, however it exhibits narrowing with increasing cluster size. The smooth evolution of the spectra shows that the clusters are composed of a dimer anion core surrounded by neutral molecules. The analysis of the fragmentation products reveals that the absorption of a photon is followed by statistical evaporation of neutrals with a mean energy loss of 0.28±0.05 eV per evaporated monomer in the large cluster limit. 相似文献
64.
65.
Brunner H Cattey H Meier W Mugnier Y Stückl AC Wachter J Wanninger R Zabel M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(16):3796-3802
The reaction of the cluster salts [Cp(2*) Nb(CO)(2)](n)[Co(11)Te(7)(CO)(10)] (Cp*=C(5)Me(5); n=1, 2) with excess PMe(2)Ph gave the neutral, dark brown clusters [Co(11)Te(7)(CO)(6)(PMe(2)Ph)(4)] (5) and [Co(11)Te(7)(CO)(5)(PMe(2)Ph)(5)] (6) with 147 metal valence electrons. The new compounds were characterized by IR spectroscopy, elemental analyses, and mass spectrometry. The molecular structure of 6 was determined by X-ray crystallography. Like its precursor anion, it consists of a pentagonal-prismatic [Co(11)Te(7)] core, but with a ligand sphere composed of five CO and five PMe(2)Ph ligands. Detailed electrochemical studies of both reactions reveal that a stepwise substitution of CO ligands in the initial cluster anions takes place leading to intermediate [Co(11)Te(7)(CO)(10-m)(PMe(2)Ph)(m)](n-) ions (m=1-5; n=1, 2). Each of these intermediates is distinguished by at least one oxidation and two reduction waves, giving rise to a total of 21 redox couples and 27 electroactive species. The electron sponge character of the new compounds is particularly pronounced in 5, which exhibits charges n between +1 and -4 corresponding to metal valence electron counts of between 146 and 151. 相似文献
66.
Günter Haufe Manfred Mühlstädt Dr. Jürgen Graefe 《Monatshefte für Chemie / Chemical Monthly》1977,108(4):803-811
In addition totrans-2-bromocyclooctanol andtrans-1,2-dibromocyclooctane,cis-4-bromocyclooctanol,cis-1,4-dibromocyclooctane,trans-1,4-dibromocyclooctane, and (Z)-5-bromocyclooctene are obtained, when (Z)-cyclooctene is treated with N-bromosuccinimide in the presence of water. Similarly the methoxybromination of (Z)-cyclooctene gives transanular products. 相似文献
67.
Gbor Nray-Szab Gyrgy Kramer Pter Nagy Sndor Kugler 《Journal of computational chemistry》1987,8(4):555-561
Computer programs have been developed or are under development for the IBM personal computer that enable their users to get information on atomic charges, electrostatic potentials, conformational and other properties of molecular systems containing H, C, N, O, F, Si, P, S, or Cl atoms. The zero-order wavefunction is constructed of strictly localized molecular orbitals with fixed atomic orbital coefficients. The wave function can be refined by optimizing these coefficients, i.e., considering inductive effects via a coupled set of 2 × 2 secular equations within the CNDO /2 approximation. Delocalization and exchange effects are accounted for by expanding the wavefunction on a basis of the aforementioned strictly localized orbitals, instead of conventional atomic orbitals, and solving the corresponding SCF equations. Our method has been applied to the study of large systems. We calculated the electrostatic field of the complex of β-trypsin and basic pancreatic trypsin inhibitor and it has been found that strong field regions more or less coincide with hydration sites. A further potential application of protein electrostatic fields is in NMR spectroscopy. We found a linear correlation between CαH or backbone NH proton chemical shifts and the protein field at the site of the corresponding proton. At last, we propose a simple method to mimic the bulk around atomic clusters modeling crystalline and amorphous silicon. Based on this method we found a linear correlation between atomic net charges and bond angle distortions in silicon clusters with 35 atoms. 相似文献
68.
Determination of Molecular Weights by Gel Chromatography of Oligoimidoamides of Phosphoric Acid. Oligoimidoamides of phosphoric acid were eluted with nonionic water on a Sephadex LH-20 column. The measured distribution coefficient of the oligoimidoamides of phosphoric acid was independent of sample concentration and pH of the eluent. Andrews equation was obeyed: a linear relation exist between elution volume and logarithm of molecular weight both cyclic and acyclic oligoimidoamides of phosphoric acid. 相似文献
69.
Breher F Rüegger H Mlakar M Rudolph M Deblon S Schönberg H Boulmaâz S Thomaier J Grützmacher H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(3):641-653
The formation of adducts of the square-planar 16-electron complexes trans-[M(tropp(ph))(2)](+) and cis-[M(tropp(ph))(2)](+) (M=Rh, Ir; tropp(Ph)=5-diphenylphosphanyldibenzo[a,d]cycloheptene) with acetonitrile (acn) and Cl(-), and the redox chemistry of these complexes was investigated by various physical methods (NMR and UV-visible spectroscopy, square-wave voltammetry), in order to obtain some fundamental thermodynamic and kinetic data for these systems. A trans/cis isomerization cannot be detected for [M(tropp(ph))(2)](+) in non-coordinating solvents. However, both isomers are connected through equilibria of the type trans-[M(tropp(ph))(2)](+)+L<==>[ML(tropp(ph))(2)](n)<==>cis-[M(tropp(ph))(2)](+)+L, involving five-coordinate intermediates [ML(tropp(ph))(2)](n) (L=acn, n=+1; L=Cl(-), n=0). Values for K(d) (K(f)), that is, the dissociation (formation) equilibrium constant, and k(d) (k(f)), that is, the dissociation (formation) rate constant, were obtained. The formation reactions are fast, especially with the trans isomers (k(f)>1x10(5) m(-1) s(-1)). The reaction with the sterically more hindered cis isomers is at least one order of magnitude slower. The stability of the five-coordinate complexes [ML(tropp(ph))(2)](n) increases with Ir>Rh and Cl(-)>acn. The dissociation reaction has a pronounced influence on the square-wave (SW) voltammograms of trans/cis-[Ir(tropp(ph))(2)](+). With the help of the thermodynamic and kinetic data independently determined by other physical means, these reactions could be simulated and allowed the setting up of a reaction sequence. Examination of the data obtained showed that the trans/cis isomerization is a process with a low activation barrier for the four-coordinate 17-electron complexes [M(tropp(ph))(2)](0) and especially that a disproportionation reaction 2 trans/cis-[M(tropp(ph))(2)](0)-->[M(tropp(ph))(2)](+)+[M(tropp(ph))(2)](-) may be sufficiently fast to mask the true reactivity of the paramagnetic species, which are probably less reactive than their diamagnetic equilibrium partners. 相似文献
70.
In the past few years millimeter and submillimeter wave spectroscopy has been the backbone for modern molecular line astronomy. The detection of unstable and high-temperature molecular species in the interstellar environment has stimulated the development of methods of detecting molecular ions, radicals and unstable molecules in the laboratory by means of millimeter wave technology. Some of the recent experimental advances as well as the developments which have occurred in the analysis of high resolution rotational and vibrational spectra with regard to understanding molecular dynamics will be discussed. 相似文献