全文获取类型
收费全文 | 2790篇 |
免费 | 60篇 |
国内免费 | 53篇 |
专业分类
化学 | 1952篇 |
晶体学 | 15篇 |
力学 | 56篇 |
数学 | 513篇 |
物理学 | 367篇 |
出版年
2021年 | 21篇 |
2017年 | 17篇 |
2016年 | 50篇 |
2015年 | 29篇 |
2014年 | 57篇 |
2013年 | 109篇 |
2012年 | 97篇 |
2011年 | 135篇 |
2010年 | 58篇 |
2009年 | 47篇 |
2008年 | 108篇 |
2007年 | 122篇 |
2006年 | 80篇 |
2005年 | 104篇 |
2004年 | 88篇 |
2003年 | 67篇 |
2002年 | 56篇 |
2001年 | 21篇 |
2000年 | 24篇 |
1999年 | 22篇 |
1998年 | 23篇 |
1997年 | 31篇 |
1996年 | 30篇 |
1995年 | 29篇 |
1994年 | 28篇 |
1992年 | 26篇 |
1991年 | 34篇 |
1990年 | 25篇 |
1989年 | 21篇 |
1988年 | 38篇 |
1987年 | 48篇 |
1986年 | 36篇 |
1985年 | 48篇 |
1984年 | 49篇 |
1983年 | 35篇 |
1982年 | 39篇 |
1981年 | 44篇 |
1980年 | 37篇 |
1979年 | 39篇 |
1978年 | 70篇 |
1977年 | 50篇 |
1976年 | 53篇 |
1975年 | 24篇 |
1974年 | 41篇 |
1973年 | 38篇 |
1972年 | 22篇 |
1971年 | 16篇 |
1969年 | 16篇 |
1885年 | 23篇 |
1884年 | 26篇 |
排序方式: 共有2903条查询结果,搜索用时 15 毫秒
21.
22.
Iodine monofluorosulfate has been found to react with fluoroolefins in the absence of a solvent to give the corresponding iodo alkyl fluorosulfates by addition of ?l and ?OSO2F across the double bond. The observed products were ICF2CF2SO3F, CF3CFlCF2SO3F, and the isomer mixture ICF2CFClSO3F and ICFClCF2SO3F. Perfluorocyclobutene was unreactive. The iodine fluorosulfate used for this study was synthesized from the reactions of either I2 or RfI with ClSO3F, with both reactions being new routes to this compound. These iodo fluorocarbon fluorosulfates are novel compounds and were characterized by spectroscopy and by formation of the derivatives CF3CFICFO and ICF2CFO. 相似文献
23.
24.
By density functional methods we characterize the bonding and charge distribution in complexes of benzene with dearomatizing agents tpReCO(L), tpMoNO(L), and tpWNO(L), where tp = hydrido Tris (pyrazolyl)borate), for a range of ligands L. Our LSDA and B3LYP density functional calculations use the Spartan LACVP+ basis and pseudopotential on Re, Mo, and W and 6-31G* on light atoms. The binding energy is strongly dependent on the nature of the ligand L, being greatest for L = ammonia and N-methylimidazole and weakest for CH3NC and CO. We find a correlation between strength of binding and electron transfer from the dearomatizing agents toward benzene. For the most strongly bound systems we find substantial (up to 500 millielectrons) charge transfer towards benzene, while for the most weakly bound systems charge is withdrawn from benzene. Structural details illustrate the ability of Re, Mo, and W species to dearomatize complexed benzene, which is extensive for all but the most weakly bound species with L = MeNC and CO. Re and W dearomatizing agents, which are computed and observed to form stable complexes with benzene, may be economic alternatives to osmium dearomatizing agents. 相似文献
25.
26.
27.
We have developed bond additivity correction (BAC) procedures for the G3-based quantum chemistry methods, G3B3 and G3MP2B3. We denote these procedures as BAC-G3B3 and BAC-G3MP2B3. We apply the procedures to compounds containing atoms from the first three rows of the periodic table including H, B, C, N, O, F, Al, Si, P, S, and Cl atoms. The BAC procedure applies atomic, molecular, and pairwise bond corrections to theoretical heats of formation of molecules. The BAC-G3B3 and BAC-G3MP2B3 procedures require parameters for each atom type but not for each bond type. These parameters have been obtained by minimizing the error between the BAC-G3B3 and BAC-G3MP2B3 predictions and the experimental heats of formation for a 155 molecule reference set, containing open and closed shell molecules representing various functional groups, multireference configurations, isomers, and degrees of saturation. As compared to former BAC-MP4, BAC-G2, and BAC-hybrid methods, BAC-G3B3 provides better agreement with experiment for a wider range of chemical moieties, including highly oxidized species involving SOx s, NOx s, POx s, and halogens. The BAC-G3B3 and BAC-G3MP2B3 procedures are applied to an extended test suite involving 273 compounds. We assess the overall quality of BAC-G3B3 with experiments and other theoretical approaches. For the reference set, the average error for the BAC-G3B3 results is 0.44 kcal/mol as compared to 0.82 kcal/mol for the raw G3B3. For the extended test set, the average error for the BAC-G3B3 results is 0.91 kcal/mol as compared to 1.38 kcal/mol for the raw G3B3. As compared to the other BAC procedures, the improved predictive capability of BAC-G3B3 and BAC-G3MP2B3 procedures is, to a large extent, due to the improved quality of G3-based methods resulting in much smaller BAC correction terms. 相似文献
28.
Carl H. Brans 《General Relativity and Gravitation》1987,19(9):949-952
It is pointed out that the field equations in one of Barber's two self-creation cosmologies are not only in disagreement with experiment, but are actually inconsistent, in general. The construction of consistent general relativistic field equations involving field variables, such as, without invoking Lagrangian techniques, requires careful checking that sufficient functional freedom has been provided so as to produce a consistent set of equations. 相似文献
29.
Wolfgang A. Herrmann Carl Krüger Richard Goddard Ivan Bernal 《Journal of organometallic chemistry》1977,140(1):73-89
μ-Carbonylbis(carbonyl-ν5-cycopentadienylrhodium)(Rh—Rh) reacts with N-methyl-and N-ethyl-N-nitrosourea in boiling benzene to yield the dinuclear, diamagnetic, neutral rhodium complexes μ-methylene- (A) and μ-ethylidenebis(carbonyl-η5-cyclopentadienylrhodium)(Rh—Rh) (B), respectively. Deuterium labelled experiments prove the origin of the metal-stabilized methylene ligand to be the alkyl group of the organic precursor. This new method of preparation of transition metal—methylene complexes may be used as an alternative to the commonly used diazo method; the latter method was shown to work with diazodiethylmalonate and dicarbonyl-η5-cyclopentadienylrhodium, the reaction yielding μ-bis(ethoxycarbonyl)methylenebis(carbonyl-η5-cyclopentadienylrhodium)(Rh—Rh).Compound A crystallizes in the triclinic system, P, and with cell constants of a 803.42(5), b 909.98(6), c 938.81(2) pm, α 74.402(3), β81.923(3), and γ 83.685(6)°. The unit cell volume and the calculated density are 651.6 Å3 and 2.069 g cm-3, for one molecule in the asymmetric unit. The molecular geometry of μ-CH2[η5-C5H5Rh(CO)]2 was established from 2718 unique reflections collected with a computer-controlled diffractometer and refined to a final R(F) = 0.0379. The molecular parameters derived from the single-crystal X-ray study conform to a remarkable degree with those found for μ-CO[η5-C5H5Rh(CO)]2. Thus, the bridging ligands CH2 and CO seem to be analogous in their effects on the structural characteristics of the molecular framework of the two molecules. 相似文献
30.
Asymmetric syntheses of (2S,3S)-3-(tert-butoxycarbonyl)-2-piperidinecarboxylic acid (1b), (3R,4S)-4-(tert-butoxycarbonyl)-3-piperidinecarboxylic acid (2b), and their corresponding N-Boc and N-Cbz protected analogues 8a,b and 17a,b are described. Enantiomerically pure 1b has been synthesized in five steps starting from L-aspartic acid beta-tert-butyl ester. Tribenzylation of the starting material followed by alkylation with allyl iodide using KHMDS produces the key intermediate 5a in a 6:1 diastereomeric excess. Upon hydroboration, the alcohol 6a is oxidized, and the resulting aldehyde 7 is subjected to a ring closure via reductive amination, providing 1b in an overall yield of 38%. Optically pure 2b has been synthesized beginning with N-Cbz-beta-alanine. The synthesis involves the induction of the first stereogenic center using Evans's chemistry and sequential LDA-promoted alkylations with tert-butyl bromoacetate and allyl iodide. Further elaboration by ozonolysis and reductive amination affords 2b in an overall yield of 28%. 相似文献