全文获取类型
收费全文 | 12926篇 |
免费 | 954篇 |
国内免费 | 1078篇 |
专业分类
化学 | 5533篇 |
晶体学 | 116篇 |
力学 | 909篇 |
综合类 | 96篇 |
数学 | 2318篇 |
物理学 | 4178篇 |
无线电 | 1808篇 |
出版年
2024年 | 17篇 |
2023年 | 104篇 |
2022年 | 172篇 |
2021年 | 195篇 |
2020年 | 289篇 |
2019年 | 241篇 |
2018年 | 256篇 |
2017年 | 353篇 |
2016年 | 424篇 |
2015年 | 355篇 |
2014年 | 667篇 |
2013年 | 860篇 |
2012年 | 788篇 |
2011年 | 890篇 |
2010年 | 739篇 |
2009年 | 906篇 |
2008年 | 855篇 |
2007年 | 910篇 |
2006年 | 878篇 |
2005年 | 649篇 |
2004年 | 550篇 |
2003年 | 533篇 |
2002年 | 431篇 |
2001年 | 308篇 |
2000年 | 309篇 |
1999年 | 259篇 |
1998年 | 208篇 |
1997年 | 218篇 |
1996年 | 205篇 |
1995年 | 154篇 |
1994年 | 170篇 |
1993年 | 125篇 |
1992年 | 122篇 |
1991年 | 115篇 |
1990年 | 88篇 |
1989年 | 73篇 |
1988年 | 65篇 |
1987年 | 62篇 |
1986年 | 45篇 |
1985年 | 48篇 |
1984年 | 62篇 |
1983年 | 15篇 |
1982年 | 42篇 |
1981年 | 37篇 |
1980年 | 24篇 |
1979年 | 31篇 |
1977年 | 25篇 |
1976年 | 15篇 |
1974年 | 17篇 |
1973年 | 15篇 |
排序方式: 共有10000条查询结果,搜索用时 11 毫秒
161.
Band structure calculations at the level of LMTO-ASA provide insight into the electronic structure of BaV10O15 and the origin of the structural phase transition. A crystal orbital Hamiltonian population/integrated crystal orbital Hamiltonian population analysis provides evidence that the crystallographic phase transition is driven by V-V bond formation. As well, the energy bands near the Fermi level are very narrow, <1 eV, consistent with the fact that the observed insulating behavior can be due to electron localization via either Mott-Hubbard correlation and/or Anderson disorder. The partial solid solution, BaV10−xTixO15, was examined to study the effect of Ti-doping at the V sites on the structure and electronic transport properties. In spite of the non-existence of “BaTi10O15”, the limiting x=8, as indicated by a monotonic increase in the cell volume and systematic changes in properties. This limit may be due to the difficulty of stabilizing Ti2+ in this structure. For x=0.5 both the first order structural phase transition and the magnetic transition at 40 K are quenched. The samples obey the Curie-Weiss law to x=3 with nearly spin only effective moments along with θ values which range from −1090 K (x=0.5) to −1629 K (x=3). For x>3 a very large, ∼2×10−3 emu/mol, temperature independent (TIP) contribution dominates. Conductivity measurements on sintered, polycrystalline samples show semiconducting behavior for all compositions. Activation energies for Mott hopping derived from high temperature data range from ∼0.1 eV for x=0-1 and fall to a plateau of 0.06 eV for x=3-7. Low temperature data for x=3, 5 and 7 show evidence for Mott variable range hoping (VRH) with a T1/4 law and in one case between 5 and 17 K, a Efros-Shklovskii correlated hopping, T1/2 law, was seen, in sharp contrast to BaV10O15 where only the E-S law was observed up to 75 K. Seebeck coefficients are small (<35 μV/K), positive, roughly TIP and increase with increasing x up to x=5. This may point to a Heikes hopping of holes but a simple single carrier model is impossible. The compositions for x>3 are remarkable in that local moment behavior is lost, yet a metallic state is not reached. The failure of this system to be driven metallic even at such high doping levels is not fully understood but it seems clear that disorder induced carrier localization plays a major role. 相似文献
162.
Yoshida H. Yang M. Masaka K. Houshito Y. Mashiko K. Nakamura S. 《Journal of Thermal Analysis and Calorimetry》2002,70(3):703-711
Phase transition behavior of polyesters derived from 2,7-phenanthrene dicarbonic acid diethylester and alkanediols with even
methylene carbon number was investigated by the simultaneous DSC-XRD method. The smectic A phase was observed on cooling from
the molten state. The transition entropy from the isotropic state to the smectic A phase was about 9.0 J mol-1 K-1, which depended on the methylene carbon number. The linear expansion coefficients, based on the (001) spacing of the crystalline
phase at room temperature, were 1.3·10-4 K-1 (crystalline phase), 5.7·10-4 K-1 (crystallization region), 1.7·10-3 K-1 (smectic A phase) during cooling, and 1.5·10-4 K-1 (crystalline phase), and 1.0·10-3K-1(melting region) on heating.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
163.
164.
K3 [Fe(CN)6] and KFe[Fe(CN)6] are classical coordination compounds. However, the mechanism of decomposition reactions has not been well expounded. The gas products of thermal decomposition were examined by gas chroma tography (GC) , and the structure of the solid products by Mossbauer spectroscopy(MS) and X-ray diffraction(XRD). The findings are explained in terms of the theory of coordination chemistry and a decomposition mechanism is proposed in this study. On the basis of various experimental results, the first stage of the decomposition of K3[Fe(CN)6] in He was found to be the evolution of(CN)2 resulting in the reduction of Fe(Ⅲ)12K3 [Fe(CN)6]→9K4[Fe(CN)6] + Fe2 [Fe(CN)6] + 6 ( CN )For KFe [Fe(CN) 6 ], the first stage of decomposition man be represented as6KFe[Fe(CN)6]→3K2Fe[Fe(CN)6] + 2Fe2[Fe(CN)6 + 3(CN)2At higher temperatures, the decomposition of both K3[Fe(CN)6) andKFe[Fe(CN)6] to form KCN and Fe2C was accomplished by the release of(CN)2 and N2. 相似文献
165.
166.
固相热分解反应最可几机制的判断 总被引:1,自引:0,他引:1
固相热分解反应最可几机制的判断高永煜,邹文樵,冯仰婕(华东理工大学化学系上海200237)关键词热分解,动力学方程,反应机制固相热分解反应机制的判断,是热分析动力学中令人感兴趣的领域。常用的方法是从含机制函数的非等温积分动力学方程出发,分别用Sest... 相似文献
167.
Danuta Wrbel Andrzej Boguta 《Journal of photochemistry and photobiology. A, Chemistry》2002,150(1-3):67-76
In this paper we describe conversion of light energy into electric energy in a photoelectrochemical cell containing zinc phthalocyanine (ZnPc) dyes. For all dyes investigated in liquid polyvinyl alcohol with dimethyl sulfoxide solution and located in the photoelectrochemical cell the following measurements have been done: absorption, fluorescence, photoacoustic spectra, photovoltaic spectra, kinetics of photocurrent and current–voltage characteristics. It has been shown that all dyes located in the photoelectrochemical cell are able to convert light into electric energy but with different effectiveness. The influence of substituted different peripheral groups to ZnPc core and the correlation between the molecular structure and effectiveness of solar to electric energy conversion were observed and described. The unique behavior of ZnPc substituted with fluorines was indicated. 相似文献
168.
The thermal behaviour of [Ba(C2H6O2)4][Sn(C2H4O2)3] used as a BaSnO3 precursor, and its phase evolution during thermal decomposition are described. The initially formed transient barium tin oxycarbonate phase disintegrates into BaCO3 and SnO2, reacting subsequently to BaSnO3. The existence of the intermediate oxycarbonate phase is evidenced by Fourier transformed infrared (FT-IR), X-ray powder diffraction (XRD) and electron energy loss spectroscopy (EELS (ELNES)) investigations. 相似文献
169.
Hilary E. Kent Terence H. Lilley Peter J. Milburn Michael Bloemendal Gus Somsen 《Journal of solution chemistry》1985,14(2):101-115
Enthalpies of dilution of the N-acetyl amides of glycine, L-alanine, L-valine, L-leucine, and L-phenylalanine, dissolved in N,N-dimethylformamide (DMF) as a solvent have been measured at 25°C. The results obtained have been analyzed to give the enthalpic interaction (or virial) coefficients of the solutes and these are compared with information previously obtained in aqueous systems. There are marked differences in the interaction properties in the two solvents and, while the additivity approach of Savage and Wood is applicable to the solutes in water it is not suitable for representing the interactions in DMF. A correlation is presented between the enthalpic second virial coefficients in DMF and the propensity of side-chains to be in proximity in globular proteins. 相似文献
170.
J. Borrs R. Carballo A. Castieiras M. C. Gmez‐Conde M. C. Fernndez‐Vidal J. Nicls 《无机化学与普通化学杂志》2005,631(11):2221-2226
Four new dinuclear copper(II) complexes have been synthesized and have the general formula [Cu2(L)(H2O)2], where L = GLYDTO [N,N′‐bis(carboxymethyl)dithiooxamide], ALADTO [N,N′‐bis(carboxyethyl)dithiooxamide], VALDTO [N,N′‐bis(1‐carboxy‐2‐methylpropyl)dithiooxamide] and LEUDTO [N,N′‐bis(1‐carboxy‐3‐methylbutyl)dithiooxamide]. The complexes were characterized by elemental analysis as well as by IR, electronic and EPR spectroscopy. These techniques provided evidence for the presence of the CuNO2S chromophore. Magnetic susceptibility measurements on all the complexes in the range 4–300 K show the existence of a dominant antiferromagnetic interaction with ?J values greater than 300 cm?1. Thermal decomposition behaviour of the complexes was studied by thermogravimetry. 相似文献