全文获取类型
收费全文 | 1058篇 |
免费 | 59篇 |
国内免费 | 7篇 |
专业分类
化学 | 814篇 |
晶体学 | 4篇 |
力学 | 20篇 |
数学 | 138篇 |
物理学 | 148篇 |
出版年
2024年 | 2篇 |
2023年 | 19篇 |
2022年 | 18篇 |
2021年 | 31篇 |
2020年 | 39篇 |
2019年 | 28篇 |
2018年 | 23篇 |
2017年 | 18篇 |
2016年 | 31篇 |
2015年 | 39篇 |
2014年 | 29篇 |
2013年 | 49篇 |
2012年 | 80篇 |
2011年 | 95篇 |
2010年 | 41篇 |
2009年 | 23篇 |
2008年 | 71篇 |
2007年 | 69篇 |
2006年 | 72篇 |
2005年 | 65篇 |
2004年 | 50篇 |
2003年 | 32篇 |
2002年 | 37篇 |
2001年 | 11篇 |
2000年 | 11篇 |
1999年 | 10篇 |
1998年 | 6篇 |
1997年 | 9篇 |
1996年 | 10篇 |
1995年 | 4篇 |
1994年 | 4篇 |
1993年 | 5篇 |
1992年 | 5篇 |
1991年 | 5篇 |
1990年 | 5篇 |
1989年 | 4篇 |
1988年 | 12篇 |
1987年 | 6篇 |
1986年 | 3篇 |
1985年 | 5篇 |
1984年 | 6篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1980年 | 8篇 |
1977年 | 5篇 |
1976年 | 2篇 |
1975年 | 4篇 |
1970年 | 2篇 |
1957年 | 2篇 |
1874年 | 1篇 |
排序方式: 共有1124条查询结果,搜索用时 15 毫秒
1.
Emily S. Tepe Ellen S. Deutsch MD Quiana Sampson Stephen Lawless James S. Reilly Robert Thayer Sataloff 《Journal of voice》2002,16(2):244-250
The objective of this study was to determine the incidence of vocal problems in young choir singers and to correlate vocal problems with demographic and behavioral information. A questionnaire addressing vocal habits and hygiene was offered to 571 young choir singers, up to 25 years of age, who sing at least weekly; 129 (22.6%) responded. More than one-half of the respondents had experienced vocal difficulty, particularly older adolescents. Detrimental behaviors and circumstances surveyed were not reflective of the incidence of vocal difficulty, except for morning hoarseness, chronic fatigue, insomnia, and female gender after puberty. Voice care professionals should be aware that self-reported voice difficulties are common among young choral singers, especially postpubescent girls, and children with symptoms consistent with reflux (morning hoarseness) and emotional stress (insomnia). Laryngologists should communicate with choral conductors and singing teachers to enhance early identification and treatment of children with voice complaints, and to develop choral educational strategies that help decrease their incidence. 相似文献
2.
Ramnial T McKenzie I Gorodetsky B Tsang EM Clyburne JA 《Chemical communications (Cambridge, England)》2004,(9):1054-1055
One-electron oxidation of N-heterocyclic carbenes (NHCs) has been carried out using oxidising agents such as tetracyanoethylene (TCNE) and ferrocenium [Cp(2)Fe](+); the formation of carbene radical cations is postulated. 相似文献
3.
G. S. Chandler 《International journal of quantum chemistry》1977,11(4):685-694
It is shown that a substantial energy improvement is gained by the variational use of Hulthén orbitals, instead of single Slater orbitals, in the 3d shells of some excited configurations of sulphur and phosphorus. The energies obtained are close to those attained with two-term Slater functions. In some cases the radial distribution functions from Hulthén orbitals are as good an approximation of SCF radial distributions as those from two-term Slater orbitals. Single term 2d functions with only one parameter are found to give almost identical energies and radial distribution functions as those obtained from two-parameter Hulthén orbitals. It is shown that the relationship between one-term 2d orbitals and Hulthén orbitals gives a method of enforcing nuclear cusp conditions on the former with little effect on the energy. 相似文献
4.
Christopher J. Chandler Leslie W. Deady James A. Reiss Vasilios Tzimos 《Journal of heterocyclic chemistry》1982,19(5):1017-1019
The preparation of a series of macrocycles, formed by reaction of HO-(-CH2-CH2-O-)nH with 1,10-phenanthroline-2,9-dicarbonyl chloride (n = 2,3,4) and 1,8-naphthyridine-2,7-dicarbonyl chloride (n = 3,4), is described. An improved synthetic route to 2,7-dimethyl-1,8-naphthyridine 9 is also reported. 相似文献
5.
In this article we derive a segment-level formula for the matrix elements of the U(2n) generators in a basis symmetry adapted to the subgroup U(n) × U(2) (i.e., spin-orbit basis), for the representations appropriate to many-electron systems. This enables the direct evaluation of the matrix elements of spin-dependent Hamiltonians. 相似文献
6.
Mueller JA Cowell A Chandler BD Sigman MS 《Journal of the American Chemical Society》2005,127(42):14817-14824
A kinetic investigation into the origin of enantioselectivity for the Pd[(-)-sparteine]Cl(2)-catalyzed aerobic oxidative kinetic resolution (OKR) is reported. A mechanism to account for a newly discovered chloride dissociation from Pd[(-)-sparteine]Cl(2) prior to alcohol binding is proposed. The mechanism includes (1) chloride dissociation from Pd[(-)-sparteine]Cl(2) to form cationic Pd(-)-sparteine]Cl, (2) alcohol binding, (3) deprotonation of Pd-bound alcohol to form a Pd-alkoxide, and (4) beta-hydride elimination of Pd-alkoxide to form ketone product and a Pd-hydride. Utilizing the addition of (-)-sparteine HCl to control the [Cl(-)] and [H(+)] and the resulting derived rate law, the key microscopic kinetic and thermodynamic constants were extracted for each enantiomer of sec-phenethyl alcohol. These constants allow for the successful simulation of the oxidation rate in the presence of exogenous (-)-sparteine HCl. A rate law for oxidation of the racemic alcohol was derived that allows for the successful prediction of the experimentally measured k(rel) values when using the extracted constants. Besides a factor of 10 difference between the relative rates of beta-hydride elimination for the enantiomers, the main enhancement in enantiodetermination results from a concentration effect of (-)-sparteine HCl and the relative rates of reprotonation of the diastereomeric Pd-alkoxides. 相似文献
7.
The atomistic origin of fatigue failure in micron-sized silicon devices is not fully understood. Two series of density-functional theory calculations on cubic diamond Si explore the effect of surface bond formation on crack healing in systems which exhibit strong surface reconstruction. Both series introduce a separation between Si(100) layers (i.e., the crack) and allow the ions to relax to their minimum-energy configuration. The initial surface ionic positions are either bulk terminated or 2 x 1 reconstructed. A plot of the energy versus the introduced separation reveals that once the surfaces reconstruct, the crack is no longer able to return to the equilibrium configuration. Rather, the healed crack interface contains defects which places the flawed energy minimum at a finite strain of 3% and an increased energy of 1.13 Jm2 relative to the equilibrium configuration. The irreversible plastic deformation supports the mechanism proposed by Kahn et al. [Science 298 1215 (2002)] that invokes mechanically induced subcritical cracking to explain the delayed onset of failure. 相似文献
8.
By combining a first-principles periodic density functional theory calculation of adsorbate resonance widths with a many-body dynamical theory of charge transfer, we assess charge-transfer rates for ions scattering off metal surfaces. This goes beyond previous approaches, which have been limited to modeling the surfaces with either static potentials or finite clusters. Here we consider Li(+) scattering from an Al(001) surface. We show how the Li 2s orbital hybridizes with metal valence bands, near the surface, increasing the width of the 2s energy level. This in turn affects the charge-transfer rates between the ion and the metal surface. Our predictions for Li(+)-Al(001) scattering yield the correct angular dependence of the fraction of neutral Li atoms formed when compared to experiment. 相似文献
9.
10.