全文获取类型
收费全文 | 6673篇 |
免费 | 158篇 |
国内免费 | 45篇 |
专业分类
化学 | 4616篇 |
晶体学 | 71篇 |
力学 | 151篇 |
数学 | 647篇 |
物理学 | 945篇 |
无线电 | 446篇 |
出版年
2023年 | 30篇 |
2022年 | 49篇 |
2021年 | 58篇 |
2020年 | 83篇 |
2019年 | 98篇 |
2018年 | 72篇 |
2017年 | 50篇 |
2016年 | 136篇 |
2015年 | 118篇 |
2014年 | 131篇 |
2013年 | 296篇 |
2012年 | 395篇 |
2011年 | 484篇 |
2010年 | 245篇 |
2009年 | 221篇 |
2008年 | 424篇 |
2007年 | 477篇 |
2006年 | 465篇 |
2005年 | 453篇 |
2004年 | 423篇 |
2003年 | 331篇 |
2002年 | 291篇 |
2001年 | 95篇 |
2000年 | 79篇 |
1999年 | 81篇 |
1998年 | 84篇 |
1997年 | 59篇 |
1996年 | 94篇 |
1995年 | 64篇 |
1994年 | 63篇 |
1993年 | 43篇 |
1992年 | 44篇 |
1991年 | 50篇 |
1990年 | 45篇 |
1989年 | 38篇 |
1988年 | 39篇 |
1987年 | 38篇 |
1986年 | 41篇 |
1985年 | 57篇 |
1984年 | 56篇 |
1983年 | 50篇 |
1982年 | 49篇 |
1981年 | 49篇 |
1980年 | 45篇 |
1979年 | 49篇 |
1978年 | 51篇 |
1977年 | 41篇 |
1976年 | 38篇 |
1975年 | 23篇 |
1974年 | 25篇 |
排序方式: 共有6876条查询结果,搜索用时 15 毫秒
11.
Brian F.G. Johnson Jack Lewis Martyn V. Twigg 《Journal of organometallic chemistry》1974,67(3):C75-C76
Photolysis of Ru3(CO)12 in the presence of donor ligands rapidly produces monomeric ruthenium species. 相似文献
12.
Rh(π-C3H5)(PF3)3 (I), reacts with trifluoroacetic acid to form propene and [Rh(CF3COO)(PF3)2]2 (II). I reacts with t-butyl bromide to give [RhBr(PF3)2]2 and a mixture of propene and 2-methyl-1-propene and with n-propyl bromide to give propene and [RhBr(PF3)2]2. Rh(π-C3H5)(PPh3)2 (III), and t-butyl bromide yield propene and 2-methyl-1-propene. In these reactions a mechanism involving β-hydrogen abstraction and hydrogen migration via the metal to carbon is proposed. When III reacts with Me3SnCl the Me3Sn—moiety migrates intact to the π-allyl group. I reacts with acetyl chloride to give propene, [RhCl(PF3)2]2 and the carbonyl rhodium complex Rh2Cl2(PF3)3(CO). II does not apparently undergo phosphine ligand exchange unlike the analogous halogeno-bridged dimers. 相似文献
13.
We present the first recording of the high-resolution spectrum of an induced chiral dimer. Three conformers of the induced chiral dimers of ethanol have been observed using a pulsed molecular-beam Fourier transform microwave spectrometer. The rotational constants of the normal isotopomers of the three species have been determined to be (a) A=5113.826(5), B=1329.7214(4), and C=1257.5151(3) MHz, (b) A=5086.459(5), B=1316.6508(4), and C=1243.6329(4) MHz, and (c) A=4851.608(5), B=1369.7558(6), and C=1243.4184(4) MHz. The observed species have been assigned to calculated structures via Kraitchman double substitution analyses and ab initio calculations. The Kraitchman analyses and the fitted centrifugal distortion parameters suggest that the deuterium bond is significantly stronger than the hydrogen bond in the dimers of ethanol. 相似文献
14.
Brian Weiner 《International journal of quantum chemistry》1985,28(1):61-84
A propagator approximation scheme is presented in the context of an abstract*-algebra approach. The representation theory of such algebras is shown to play a crucial role in the definition of consistent approximations, i.e., approximate propagators based on model time evolutions and states. This procedure places superoperator methods of approximation on a sound Hilbert space footing. A generalization of the Fock vacuum property is introduced which leads to a simplification in the form of the model propagators. Finally a concrete example is considered that fulfills the conditions developed in this article showing that a consistent approximation to the electron propagator results in the Hartree–Fock–Boguliubov equations. 相似文献
15.
A computational study is made of the effect of basis set upon the energy, properties and inversion barrier of the phosphine molecule. The calculations are performed at both the SCF and CI level. The flexibility of the double zeta basis is discussed in the light of the results. 相似文献
16.
Nicole Desrosiers Gérald Perron John G. Mathieson Brian E. Conway Jacques E. Desnoyers 《Journal of solution chemistry》1974,3(10):789-806
The apparent molal volume φv, expansibility φE, compressibility φK, and heat capacity φc of NaCl were measured in urea-water mixtures, as a function of salt (<1.5m) and urea (<13m) concentrations at 25°C. At a fixed urea concentration, the transfer functions from H2O to 3m urea are linear functions of the NaCl aquamolality. At a fixed salt aquamolality, (0.1m), the sign of the transfer functions is in the direction of a decrease in the structure-breaking effect, and the absolute values of the transfer functions tend to level off at high urea concentrations (13m). The functions φv, φE, φK, φc, and (?φv/?T)p were measured for the sodium halides and alkali, bromides (chlorides in the case of φK) at a fixed salt aquamolality of 0.1m and fixed urea molality of 3m. The corresponding transfer functions from H2O to 3m urea are opposite those from H2O to D2O and similarly are relatively independent of ionic size. This suggests that urea, shows no specific interaction affinity for ions and that the overall number of water molecules influenced by the ions is relatively constant for all alkali halides. The lithium halides are an exception in that Li+ seems to have hardly any structure-breaking effect. 相似文献
17.
Nineteen sulphonated 2-hydroxybenzophenones and three sulphonated 2,2′-dihydroxybenzophenones have been prepared and compared with a commercially available member of each class of uv absorber as photo-protective agents for wool. Treated fabrics were exposed to Philips ML G/74 lamps and the extent of photo-tendering was assessed by measuring breaking loads and tear strengths. In general, 2-hydroxybenzophenones with 3-alkyl substituents provide better protection against photo-tendering than absorbers lacking 3-alkyl substituents. 2,2′-Dihydroxybenzophenones are more effective than 2-hydroxybenzophenones.
On the basis of effectiveness and ease of synthesis, 2,2′-dihydroxy-4,4′-bis-w-sulphobutyloxybenzophenone (VIIb) shows most promise as a photo-protective agent. At the 5% level of application it trebles the lifetime of wool fabric during exposure to sunlight through window glass. It also retards the photo-tendering and fading of wool fabrics containing either a red or a blue milling acid dye. 相似文献
18.
The isotropic ESR spectra of a number of phosphonyl radicals (X2O), the dimethylphosphinyl radical, and the phosphoranyl radical (MeO)3OBu-t, are described, and accurate values of the phosphorus hyperfine splittings and g-factors are reported. For X2O, the value of a(P) increases and the g-factor decreases as the electronegativity of X increases. There is a linear relationship between a(P) for X2O and 1J(PH) for X2P(O)H, but the same relationship does not hold for Me2P- and Me2PH. The spectrum of the di-n-hexylphosphonyl radical shows coupling to two pairs of α-methylene protons, and this non-equivalence is attributed to the pyramidal structure of the phosphonyl radical. 相似文献
19.
Gottfried Lichti Brian S. Hawkett Robert G. Gilbert Donald H. Napper David F. Sangster 《Journal of polymer science. Part A, Polymer chemistry》1981,19(4):925-938
Data are presented on the time evolution of particle-size distributions (PSDs) in seeded and ab initio styrene emulsion polymerization systems. Initiation was by chemical reagent (potassium persulfate) or γ-radiation. The unswollen PSDs at various times during interval II of the polymerization were obtained by direct measurement of calibrated electron micrographs. Experimental results were fitted with the equations that describe the time evolution of an initial PSD. Analytic solutions to these equations that allow for entry, exit, and propagation of free radicals were obtained. The values of the rate coefficients for these processes used to fit the experimental data were in excellent agreement with those obtained from dilatometric kinetics experiments. 相似文献
20.
Aihara H Alston-Garnjost M Bakken JA Barbaro-Galtieri A Barnes AV Barnett BA Bengtsson H Blumenfeld BJ Bross AD Buchanan CD Chamberlain O Chien C Clark AR Cordier A Dahl OI Day CT Derby KA Eberhard PH Fancher DL Fujii H Fujii T Gabioud B Gary JW Gorn W Hadley NJ Hauptman JM Hofmann W Huth JE Hylen J Kamae T Kaye HS Kenney RW Kerth LT Koda RI Kofler RR Kwong KK Layter JG Lindsey CS Loken SC Lu X Lynch GR Madansky L Madaras RJ Maruyama K Marx JN Matthews JA Melnikoff SO Moses W Nemethy P 《Physical review letters》1985,54(4):270-273