全文获取类型
收费全文 | 527篇 |
免费 | 11篇 |
专业分类
化学 | 311篇 |
力学 | 12篇 |
数学 | 73篇 |
物理学 | 142篇 |
出版年
2023年 | 7篇 |
2022年 | 7篇 |
2021年 | 12篇 |
2020年 | 13篇 |
2019年 | 6篇 |
2018年 | 6篇 |
2017年 | 9篇 |
2016年 | 17篇 |
2015年 | 18篇 |
2014年 | 23篇 |
2013年 | 35篇 |
2012年 | 32篇 |
2011年 | 28篇 |
2010年 | 16篇 |
2009年 | 17篇 |
2008年 | 32篇 |
2007年 | 27篇 |
2006年 | 33篇 |
2005年 | 27篇 |
2004年 | 26篇 |
2003年 | 12篇 |
2002年 | 12篇 |
2001年 | 8篇 |
2000年 | 5篇 |
1999年 | 10篇 |
1998年 | 2篇 |
1997年 | 8篇 |
1996年 | 5篇 |
1995年 | 9篇 |
1994年 | 8篇 |
1993年 | 6篇 |
1992年 | 10篇 |
1991年 | 5篇 |
1990年 | 4篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1980年 | 4篇 |
1975年 | 2篇 |
1973年 | 1篇 |
1970年 | 4篇 |
1969年 | 1篇 |
1911年 | 1篇 |
1906年 | 3篇 |
1905年 | 3篇 |
1904年 | 1篇 |
1903年 | 1篇 |
排序方式: 共有538条查询结果,搜索用时 15 毫秒
1.
2.
The electron-stimulated desorption (ESD) of D− and H− ions from condensed D2O and H2O films is investigated. Three low-energy peaks are observed in the ESD anion yield, which are identified as arising from excitation of 2B1, 2A1 and 2B2 dissociative electron attachment (DEA) resonances. Additional structure is observed between 18 and 32 eV, which may be due to ion pair formation or to DEA resonances involving the 2a1 orbital. The ion yield resulting from excitation of the 2B1 resonance increases as the film is heated. We attribute the increase in the ion yield to thermally induced hydrogen bond breaking near the surface, which enhances the lifetimes of the excited states that lead to desorption. 相似文献
3.
4.
Pascale F Catti M Damin A Orlando R Saunders VR Dovesi R 《The journal of physical chemistry. B》2005,109(39):18522-18527
The vibrational spectrum of Ca3Fe2Si3O12 andradite is calculated at the Gamma point by using the periodic ab initio CRYSTAL program that adopts an all-electron Gaussian-type basis set and the B3LYP Hamiltonian. The full set of frequencies (17 IR active, 25 Raman active, and 55 inactive modes) is calculated. The effect of the basis set on the calculated frequencies is discussed. The modes are characterized by direct inspection of the eigenvectors and isotopic substitution. The present calculations permit us to clarify some of the assignment problems raised by experiments. The mean absolute differences of the various modes with respect to the available experimental IR and Raman data are as small as 9 and 5 cm(-1), respectively. 相似文献
5.
Pascale F Ugliengo P Civalleri B Orlando R D'Arco P Dovesi R 《The Journal of chemical physics》2004,121(2):1005-1013
The structure of the Si-free katoite hydrogarnet (116 atoms in the unit cell) has been investigated at the periodic ab initio quantum mechanical level with the CRYSTAL program, by using a Gaussian type basis set and both the HF and the hybrid B3-LYP Hamiltonians. The structure has been fully optimized at various pressures in the 0-46 GPa range; the modifications of the structure, and in particular of the (OH)4 group, as a function of pressure are analyzed. At the B3-LYP level and P greater than 15 GPa, a O-H...O interaction of increasing strength appears, with important modifications in the local geometry of the tetrahedral site. The calculated omega01(O-H) fundamental vibrational frequency at zero pressure is in excellent agreement with experiment (3674 and 3663 cm(-1), respectively); the omega01(O-H) stretching frequency remains essentially constant in the 0-15 GPa interval, whereas it dramatically decreases at higher pressures with a corresponding anharmonicity increase, as a consequence of the formation of a strong hydrogen bond. The hydration energy of grossular and the formation energy of Si-free katoite have also been computed, and the B3-LYP results are in quite good agreement with experiment. 相似文献
6.
Chen H Aleksandrov A Chen Y Zha S Liu M Orlando TM 《The journal of physical chemistry. B》2005,109(22):11257-11262
Polycrystalline gadolinia-doped ceria (GDC) surfaces were studied using low-energy (5-400 eV) electron stimulated desorption (ESD). H(+), O(+), and H(3)O(+) were the primary cationic desorption products with H(+) as the dominant channel. H(+), H(3)O(+), and O(+) have a 22 eV threshold followed by a yield change around 40 eV. H(+) also has an additional yield change approximately 75 eV and O(+) has an additional change approximately 150 eV. The O(+) ESD yield change approximately 150 eV may indicate bond breaking of Gd-O and the involvement of oxygen vacancies. The H(+) and H(3)O(+) threshold data collectively indicate the presence of hydroxyl groups and chemisorbed water molecules on the GDC surfaces. ESD temperature dependence measurements show that the interaction of water with GDC surface defect sites, mainly oxygen vacancies, influences the desorption of H(+), O(+), and H(3)O(+). The temperature dependence of the O(+) ESD at 400 eV incident electron energy yields a 0.21 eV activation energy. This is close to the energy needed for oxygen vacancy production next to a pair of Ce(3+) on a CeO(2) surface. These results may indicate a correlation between the O(+) ESD yield and oxygen vacancy density on GDC surfaces and a potential correlation of O(+) ESD and GDC ionic conductivity. 相似文献
7.
Improta R Mele F Crescenzi O Benzi C Barone V 《Journal of the American Chemical Society》2002,124(26):7857-7865
The importance of vicinal and long-range interresidue effects in determining the stability of the collagen triple helix has been investigated by quantum mechanical (QM) and molecular mechanical (MM) computations on suitable model polypeptides, taking into account solvent effects by the polarizable continuum model (PCM). At the QM level, the PII conformation corresponds to an energy minimum for pentapeptide analogues incorporating the sequence Gly-Pro-Pro-Gly, irrespective of the down or up puckering of the pyrrolidine ring. However, our computations indicate that the alternation of down and up prolines characterizing collagen and collagen-like peptides is not due to an intrinsic preference of the Pro-Pro-Gly sequence. This result is confirmed by MM computations of longer polypeptides. Next, MM computations on model triple helices show that a better packing is obtained for specific values of backbone dihedrals, which, in turn, favor the alternation of down and up prolines along each chain. 相似文献
8.
9.
The solvent effect on 17O isotropic shielding was computed by different methods: the polarizable continuum model and a mixed approach, including a few real solvent molecules treated as the solute. The experimental data show that the behavior of protic and aprotic solvents is markedly different: we found that the continuum approach describes well the observed shielding at various dielectric constants for aprotic solvents, while the mixed procedure is needed when hydrogen bonds to the magnetic centre are present.Contribution to the Jacopo Tomasi Honorary Issue 相似文献
10.
R. C. Orlando E. A. N. Fernandes M. Szikszay 《Journal of Radioanalytical and Nuclear Chemistry》1994,179(2):259-266
This study comprises Tertiary sediments (clays, silts, and fine clayey sands) from the unsaturated zone of the Experimental Station in the University of São Paulo, taken from a nine meters depth profile; ten samples were separated in bulk and <53 m fractions. Chemical composition was determined by INAA to ascertain the distribution of trace elements throughout the sediment deposition, and to establish the background parameters, useful for mobilization studies of such elements after industrial waste disposal. 相似文献