全文获取类型
收费全文 | 6985篇 |
免费 | 915篇 |
国内免费 | 1223篇 |
专业分类
化学 | 6119篇 |
晶体学 | 43篇 |
力学 | 247篇 |
综合类 | 40篇 |
数学 | 128篇 |
物理学 | 2546篇 |
出版年
2024年 | 20篇 |
2023年 | 74篇 |
2022年 | 153篇 |
2021年 | 168篇 |
2020年 | 183篇 |
2019年 | 200篇 |
2018年 | 157篇 |
2017年 | 180篇 |
2016年 | 281篇 |
2015年 | 275篇 |
2014年 | 310篇 |
2013年 | 533篇 |
2012年 | 424篇 |
2011年 | 440篇 |
2010年 | 355篇 |
2009年 | 471篇 |
2008年 | 500篇 |
2007年 | 509篇 |
2006年 | 494篇 |
2005年 | 414篇 |
2004年 | 425篇 |
2003年 | 402篇 |
2002年 | 300篇 |
2001年 | 283篇 |
2000年 | 302篇 |
1999年 | 257篇 |
1998年 | 232篇 |
1997年 | 147篇 |
1996年 | 126篇 |
1995年 | 101篇 |
1994年 | 81篇 |
1993年 | 50篇 |
1992年 | 55篇 |
1991年 | 43篇 |
1990年 | 26篇 |
1989年 | 26篇 |
1988年 | 19篇 |
1987年 | 18篇 |
1986年 | 9篇 |
1985年 | 19篇 |
1984年 | 5篇 |
1983年 | 7篇 |
1982年 | 12篇 |
1981年 | 7篇 |
1980年 | 4篇 |
1979年 | 13篇 |
1978年 | 4篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1973年 | 5篇 |
排序方式: 共有9123条查询结果,搜索用时 15 毫秒
191.
Density functional calculations were performed on bonding and structural features of [(ηn-BH4)TM(CO)4]− (n = 1, 2, 3; TM = Cr, Mo) complexes. Calculations show that the ground state is bidentate which is in good agreement with experimental results. It has been found that the bridge and terminal hydrogen atoms will interchange by two pathways: (i) twist of BH4 about one of the bridge B-H and (ii) twist of BH4 about one of the terminal B-H. The molecular orbital calculations and natural bond orbital methodologies for different isomers of these complexes have been evaluated. The final results indicate that case (i) is more preferable relative to another case. 相似文献
192.
Ab initio supermolecular SCF calculations at the STO-3G level are reported for the diacetylene-hydrogen fluoride complexes. The reverse
σ-complex is predicted to have somewhat higher stability and H-bond strength than the π-complexes. 相似文献
193.
《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(13):3065-3072
The synthesis, spectroscopic properties, and computational analysis of an imidazole‐based analogue of porphycene are described. The macrocycle, given the trivial name “imidacene”, was prepared by reductive coupling of a diformyl‐substituted 2,2′‐biimidazole using low‐valent titanium, followed by treatment with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone. Imidacene displays a porphyrin‐like electronic structure, as judged by its 1H NMR, 13C NMR, and UV/Vis spectral characteristics. Despite a cyclic 18 π‐electron pathway, dichloromethane or ethyl acetate solutions of imidacene were found to undergo rapid decomposition, even in the absence of light and air. A series of high‐level theoretical calculations, performed to probe the origin of this instability, revealed that the presence of a delocalized 18 π‐electron pathway in both imidacene and porphycene provides less aromatic stabilization energy than locally aromatic 6 π‐electron heterocycles in their reduced counterparts. That reduction of imidacene occurs on perimeter nitrogen atoms allows it to maintain its planarity and two stabilizing intramolecular hydrogen bonds, thereby distinguishing it from porphycene and, more generally, from porphyrin. Despite the presence of both 18 π‐ and 22 π‐electron pathways in the planar, reduced form of imidacene, aromaticity is evident only in the 6 π‐electron five‐membered rings. Our computational analysis predicts that routine 1H NMR spectroscopy can be used to distinguish between local and global aromaticity in planar porphyrinoid macrocycles; the difference in the chemical shift for the internal NH protons is expected to be on the order of 19 ppm for these two electronically disparate sets of ostensibly similar compounds. 相似文献
194.
The calculations of clusters modeling the fluorine-doping and oxygen deficiency of YBa2Cu307 have been performed by the method of all-electronab initio Hartree-Fock with self-consistent crystal field. Results show that in CuO planes electric charge significantly increases,
the chemical valence of Cu decreases and the covalent bonding of Cu-O greatly weakens owing to oxygen deficiency, while the
effect of F restores the local electronic structure of YBa2Cu3O7. The reported opinion that F occupied the oxygen vacancy in Cu-O chains seems disputable according to the calculated bonding
characteristics
Project supported by the National Natural Science Foundation of China. 相似文献
195.
The force fields, in-plane vibrations, and relative intensities of Raman spectra have been calculated and analyzed for the N1H and N3H tautomers of imidazole, imidazolium cation, and their model structures. The results obtained for the isolated state of imidazole correspond to the intramolecular mechanism of proton transfer. 相似文献
196.
Bajor G Veszprémi T Riague el H Guillemin JC 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(15):3649-3656
Vinyl, allyl, and homoallyl selenols were easily prepared by a chemoselective reduction of the corresponding selenocyanates with aluminum hydrides. Two stable vinyl and five stable allyl conformers of both series were predicted on the potential-energy surface. The interaction of SeH or SeCN groups with the vinyl group has been investigated with UV photoelectron spectroscopy and quantum chemical calculations, using the MP2/cc-pVTZ and B3LYP/cc-pVTZ levels. In the vinyl derivatives, a surprisingly strong direct conjugation of the selenium lone electron pair and the C=C double bond was observed. On the other hand, in allyl position the selenium lone pair is independent on the C=C double bond, and the hyperconjugation between the Se-C bond and the double bond is the ruling effect. Thus is clarified the type and extent of the interaction between the SeH or SeCN group and the unsaturated moiety. 相似文献
197.
对于NO分子轨道的能级次序现有两种不同的说法,不少人根据NO与O_2~+是等电子体,由O_2~+分子的能级次序确定NO分子组态。本文用NO和O_2~(+)从头计算结果以及NO的紫外光电子能谱相结合的方法说明NO的5σ轨道是弱成键轨道,5σ的轨道能稍高于1π轨道能,也就是说NO的能级次序是与N_2分子相同的;NO与O_2~+虽是等电子体,但是能级次序并不相同,因此由O_2~+的能级次序确定NO分子的电子组态是不妥的。 相似文献
198.
Starting from earlier work by Baudler we introduce a chemical heuristic for the systematic deduction and classification of covalent partial structures of phosphorus in polycyclic phosphanes, phosphorus-rich polycyclic phosphides, and allotropes of phosphorus except the black forms. This approach is used to direct ab initio techniques (which also confirm the rules) in the quest for as yet unknown forms of molecular or macromolecular phosphorus. Based on calculated stabilities of systematically generated structural alternatives we rationalize the stabilities of Hittorf's phosphorus and of molecular P4, confirm the possible existence of at least one other crystalline allotropic form of phosphorus, and provide insight into the probable structure of amorphous red phosphorus. In total, the combined approach of chemical heuristics and large scale ab initio calculations presented in this work supplies a coherent chemical understanding of covalent polyphosphorus structures. 相似文献
199.
The ab initio Neglect of Differential Diatomic Overlap (N.D.D.O.) method of Roby is tested numerically for an extensive series of molecules. Agreement with the full ab initio molecular orbital method is poor. Total energies are more negative and dipole moments are overestimated. The failings of the N.D.D.O. method are accounted for using multipole-multipole expansions. 相似文献
200.
Electron and photon reflection ratios (in number and energy) for absorbers bombarded by electrons have been computed with the ITS Monte Carlo system version 3. Electrons of energies from 0.1 to 100 MeV have been assumed normally incident on an effectively semi-infinite absorber. The absorbers considered are elemental solids of atomic numbers from 4 to 92. The data on the electron reflection ratios agree rather well with the experimental data collected from literature except some discrepancies when the number-reflection ratio is small. For photons, the number-reflection ratio increases with increasing energy, but the energy-reflection ratio shows a maximum around 10 MeV. Empirical equations for the electron reflection ratios and the photon energy-reflection ratio are given (for electrons, graphs only). 相似文献