全文获取类型
收费全文 | 17306篇 |
免费 | 1743篇 |
国内免费 | 770篇 |
专业分类
化学 | 11230篇 |
晶体学 | 816篇 |
力学 | 238篇 |
综合类 | 46篇 |
数学 | 102篇 |
物理学 | 7387篇 |
出版年
2024年 | 16篇 |
2023年 | 117篇 |
2022年 | 270篇 |
2021年 | 317篇 |
2020年 | 399篇 |
2019年 | 338篇 |
2018年 | 297篇 |
2017年 | 338篇 |
2016年 | 548篇 |
2015年 | 471篇 |
2014年 | 611篇 |
2013年 | 1337篇 |
2012年 | 1052篇 |
2011年 | 1071篇 |
2010年 | 928篇 |
2009年 | 1131篇 |
2008年 | 1127篇 |
2007年 | 1381篇 |
2006年 | 1251篇 |
2005年 | 906篇 |
2004年 | 914篇 |
2003年 | 774篇 |
2002年 | 589篇 |
2001年 | 459篇 |
2000年 | 417篇 |
1999年 | 357篇 |
1998年 | 358篇 |
1997年 | 261篇 |
1996年 | 317篇 |
1995年 | 278篇 |
1994年 | 263篇 |
1993年 | 192篇 |
1992年 | 156篇 |
1991年 | 112篇 |
1990年 | 97篇 |
1989年 | 64篇 |
1988年 | 61篇 |
1987年 | 31篇 |
1986年 | 40篇 |
1985年 | 40篇 |
1984年 | 37篇 |
1983年 | 13篇 |
1982年 | 22篇 |
1981年 | 14篇 |
1980年 | 6篇 |
1979年 | 7篇 |
1977年 | 6篇 |
1975年 | 5篇 |
1974年 | 4篇 |
1973年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 187 毫秒
21.
Eldad Herceg 《Surface science》2006,600(19):4563-4571
The formation of a well-ordered p(2 × 2) overlayer of atomic nitrogen on the Pt(1 1 1) surface and its reaction with hydrogen were characterized with reflection absorption infrared spectroscopy (RAIRS), temperature programmed desorption (TPD), low energy electron diffraction (LEED), Auger electron spectroscopy (AES), and X-ray photoelectron spectroscopy (XPS). The p(2 × 2)-N overlayer is formed by exposure of ammonia to a surface at 85 K that is covered with 0.44 monolayer (ML) of molecular oxygen and then heating to 400 K. The reaction between ammonia and oxygen produces water, which desorbs below 400 K. The only desorption product observed above 400 K is molecular nitrogen, which has a peak desorption temperature of 453 K. The absence of oxygen after the 400 K anneal is confirmed with AES. Although atomic nitrogen can also be produced on the surface through the reaction of ammonia with an atomic, rather than molecular, oxygen overlayer at a saturation coverage of 0.25 ML, the yield of surface nitrogen is significantly less, as indicated by the N2 TPD peak area. Atomic nitrogen readily reacts with hydrogen to produce the NH species, which is characterized with RAIRS by an intense and narrow (FWHM ∼ 4 cm−1) peak at 3322 cm−1. The areas of the H2 TPD peak associated with NH dissociation and the XPS N 1s peak associated with the NH species indicate that not all of the surface N atoms can be converted to NH by the methods used here. 相似文献
22.
23.
Tsutomu KumagaiMasaaki Tomura Jun-ichi NishidaYoshiro Yamashita 《Tetrahedron letters》2003,44(36):6845-6848
1,3-Dithiol-2-ylidene derivatives containing bis(ethynylpyridine) units were synthesized using a Pd-catalyzed reaction of the corresponding dibromide. X-Ray crystal analysis revealed unique crystal structures depending on the aromatic groups. The absorption spectra and redox properties indicated intramolecular charge-transfer interactions between the 1,3-dithiole unit and the pyridyl parts. 相似文献
24.
Electron beam induced quantitative X-ray mapping has become a very useful characterisation tool for determining the elemental
distribution in materials, whether using energy dispersive spectroscopy or wavelength dispersive spectroscopy. The X-ray intensity
distributions of the elements from an X-ray map allow us to generate two dimensional and ternary scatter diagrams thus converting
spatial information into concentration dimensions, which is an important tool for displaying the spatial relationships of
elements or correlated elements (phases) in materials. To best understand how to use this tool, we need to understand the
production and features of the scatter diagram. The type of clustering observed in the scatter diagram, whether oval, linear
or spherical, can give the major and trace element distributions within phases as well as qualitative and quantitative phase
information. This paper demonstrates the generation of scatter diagrams, properties of scatter diagrams, interpretation of
scatter diagrams and the advantages of scatter diagrams through the use of examples. 相似文献
25.
Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η5-C5H5)Fe2+(η5-C5H4)-CH2-CH2-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe3+ at the expenses of Fe2+ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO− groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe3+ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing. 相似文献
26.
K. C. Kumara Swamy E. Balaraman M. Phani Pavan N. N. Bhuvan Kumar K. Praveen Kumar N. Satish Kumar 《Journal of Chemical Sciences》2006,118(6):495-501
The diversity of products in the reaction of diethyl azodicarboxylate (DEAD)/diisopropyl azodicarboxylate (DIAD) and activated
acetylenes with PIII compounds bearing oxygen or nitrogen substituents is discussed. New findings that are useful in understanding the nature
of intermediates involved in the Mitsunobu reaction are highlighted. X-ray structures of two new compounds (2-t-Bu-4-MeC6H3O)P (μ-N-t-Bu)2P+[(NH-t-Bu)N[(CO2]-i-Pr)(HNCO2-i-Pr)]](Cl-)(2-t-Bu-4-MeC6H3OH)(23)and [CH2(6-t-Bu-4-Me-C6H2O)2P(O)C(CO2Me)C-(CO2Me)CClNC(O)Cl] (33) are also reported. The structure of23 is close to one of the intermediates proposed in the Mitsunobu reaction. 相似文献
27.
The cocrystal of 1,2-bis(diphenylphosphinoyl)ethane (DPPEO) with phenol (1:1) were studied theoretically with AM1, PM3, MNDO and MINDO/3 semi-empirical methods to elucidate its structure. The bond lengths and angles from theoretical studies of molecule DPPEO/phenol (1:1) were found to be as expected. Theoretical results, concerning with intermolecular van der Waals forces in cocrystal, were compared with the previously obtained experimental data and AM1 results were found to be the best fit for bond lengths and angles of DPPEO/phenol. 相似文献
28.
Based on the Fourier transform method, a simple closed-form expression for the on-axis power spectrum of ultrashort Gaussian pulsed beams in diffraction at a circular aperture is derived, which permits us to study spectral changes both analytically and numerically. It is shown that for diffracted pulsed beams there exist spectral red and blue shifts, spectral narrowing, and spectral switches in the near field. The aperture diffraction plays an important role in spectral switching, but both the truncation parameter and bandwidth (or equally, Fourier transform limited pulse duration) affect the behavior of spectral switches. 相似文献
29.
The room temperature structure of perovskite CeAlO3 has been reinvestigated by X-ray powder diffraction. The Rietveld refinement has confirmed the tetragonal symmetry; but revealed a super cell, a=5.32489(6) Å and c=7.58976(10) Å, with the space group I4/mcm. In CeAlO3, the distortion from the ideal cubic perovskite is caused by the cooperative tilting of the AlO6 octahedra around the primitive cubic [001]p-axis. 相似文献
30.