全文获取类型
收费全文 | 4279篇 |
免费 | 260篇 |
国内免费 | 11篇 |
专业分类
化学 | 3140篇 |
晶体学 | 13篇 |
力学 | 95篇 |
综合类 | 1篇 |
数学 | 628篇 |
物理学 | 673篇 |
出版年
2023年 | 38篇 |
2022年 | 36篇 |
2021年 | 67篇 |
2020年 | 96篇 |
2019年 | 89篇 |
2018年 | 94篇 |
2017年 | 78篇 |
2016年 | 180篇 |
2015年 | 169篇 |
2014年 | 149篇 |
2013年 | 295篇 |
2012年 | 302篇 |
2011年 | 347篇 |
2010年 | 181篇 |
2009年 | 163篇 |
2008年 | 255篇 |
2007年 | 248篇 |
2006年 | 198篇 |
2005年 | 200篇 |
2004年 | 202篇 |
2003年 | 137篇 |
2002年 | 120篇 |
2001年 | 92篇 |
2000年 | 94篇 |
1999年 | 69篇 |
1998年 | 54篇 |
1997年 | 24篇 |
1996年 | 49篇 |
1995年 | 30篇 |
1994年 | 40篇 |
1993年 | 34篇 |
1992年 | 38篇 |
1991年 | 36篇 |
1990年 | 27篇 |
1989年 | 17篇 |
1988年 | 23篇 |
1987年 | 16篇 |
1986年 | 21篇 |
1985年 | 30篇 |
1984年 | 25篇 |
1983年 | 16篇 |
1982年 | 20篇 |
1981年 | 21篇 |
1979年 | 8篇 |
1978年 | 9篇 |
1977年 | 18篇 |
1976年 | 10篇 |
1975年 | 11篇 |
1974年 | 9篇 |
1973年 | 11篇 |
排序方式: 共有4550条查询结果,搜索用时 31 毫秒
31.
32.
B. Ritzer M.A. Villegas J.M. Fernández Navarro 《Journal of Sol-Gel Science and Technology》1997,8(1-3):917-921
The darkening of silica sol-gel glasses doped with 0.05 mol% silver was studied. Six sols were prepared from TEOS and silver
nitrate. Different additives were used, to influence the chemical and physical states of silver: oxidizing or reducing agents
(H2O2, As2O5), colloid stabilizer (sodium citrate) and network modifiers (Li2O, CaO). Sols were gelified at 60°C and densified at 600°C. The samples without additives and those prepared with H2O2 at room temperature even if they were protected from light. With increased temperature, the darkening became samples were
heated above, 400°C, reversible bleaching took place. This darkening-bleaching is of thermal nature (“thermochromic effect”)
and seems to be determined by a reversible aggregation-disaggregation of tiny silver particles. The presence of sodium citrate,
as an additive delayed the darkening effect and the presence of CaO delayed it even further. Lithium oxide inhibited it totally. 相似文献
33.
Reguera Edilso Fernández-Bertrán José Balmaseda Jorge 《Transition Metal Chemistry》1999,24(6):648-654
Evidence in the literature on the synthesis of ferrous ferricyanide is critically discussed. Pyrolysis and pressure effects on Prussian Blue lead to ferrous ferrocyanide together with decomposition by-products, and not to ferrous ferricyanide. The latter compound could be a precursor in the formation of Turnbull's Blue or an excited state of Prussian Blue, but it is not a stable chemical species. 相似文献
34.
We derive rigorously general results on the critical behavior of the magnetization in Ising models, as a function of the temperature and the external field. For the nearest-neighbor models it is shown that ind4 dimensions the magnetization is continuous atT
c and its critical exponents take the classical values=3 and=1/2, with possible logarithmic corrections atd=4. The continuity, and other explicit bounds, formally extend tod>3 1/2. Other systems to which the results apply include long-range models ind=1 dimension, with 1/|x–y|
couplings, for which 2/(–1) replacesd in the above summary. The results are obtained by means of differential inequalities derived here using the random current representation, which is discussed in detail for the case of a nonvanishing magnetic field.Research supported in part by NSF grant PHY-8301493 A02, and by a John S. Guggenheim Foundation fellowship (M.A.). 相似文献
35.
After carrying out a systematic basis set convergence study, we evaluate several ground state potential energy surfaces of the Ar-N(2) van der Waals complex at the coupled cluster singles and doubles model including connected triples corrections. We use the aug-cc-pVXZ (X=5,Q,D) and the daug-cc-pVQZ basis sets augmented with a set of 3s3p2d1f1g (denoted 33211) and 3s3p2d2f1g (denoted 33221) midbond functions, respectively. aug-cc-pVTZ-33211 results were available in the literature. The aug-cc-pV5Z-33211 (daug-cc-pVQZ-33221) surface is characterized by a T-shaped minimum at R(e)=3.709 (3.701) A and of 99.01 (102.50) cm(-1), and a linear saddle point at 4.260 (4.257) A and D(e)=75.28 (79.73) cm(-1). These results are compared with the values provided by the semiempirical potentials available, and those of previous theoretical studies. The basis set convergence of the intermolecular potentials is also analyzed. From the potentials the rovibronic spectroscopic properties are determined. We study the basis set convergence of the rotational frequencies. The binding parameters that characterized the aug-cc-pVTZ-33211 surface are reasonable, but the surface is not good enough to evaluate the microwave spectra. The aug-cc-pVQZ-33211 basis set results considerably improve the triple zeta and are close to the aug-cc-pV5Z-33211. Considering the small differences between the quadruple and the quintuple zeta surfaces, the latter results can be expected to be close to convergence. At this level the differences with respect to the accurate experimental frequencies are in the order of 0.7%. In the case of the daug-cc-pVXZ-33211,33221 (X=5,Q,T,D) series, the convergence of the interaction energies with respect to basis set improvement is not so smooth. The errors in the frequencies obtained with the daug-cc-pVQZ-33221 basis set with respect to experiment are in the order of 0.4%. 相似文献
36.
Fernández-Rivas C Méndez M Nieto-Oberhuber C Echavarren AM 《The Journal of organic chemistry》2002,67(15):5197-5201
The intramolecular reaction of allylsilanes and allylstannanes with alkynes proceeds catalytically in the presence of Pt(II), Pd(II), Ru(II), and Au(III) chlorides. Although more limited, AgOTf also catalyzes the cyclization. Usually, PtCl2 as the catalyst in methanol or acetone gives the best results. The reaction proceeds by exo attack of the allyl nucleophile on the alkyne to form five- or six-membered ring carbocycles. The reaction generally proceeds with anti stereoselectivity. However, a terminally substituted trimethylsilyl derivative reacts by a syn-type addition. The intermediate alkenylpalladium complex has been trapped with allyl chloride to form an allylated derivative with an additional carbon-carbon bond. 相似文献
37.
Héctor Beltrán Nahum Masó Beatriz Julian Eloisa Cordoncillo Juan B. Carda Purificación Escribano Anthony R. West 《Journal of Sol-Gel Science and Technology》2003,26(1-3):1061-1065
Lead Magnesium Niobate, Pb(Mg1/3Nb2/3)O3 (PMN), is an important relaxor ferroelectric material. A significant problem exists, however, in the preparation of this material: it is very difficult to prepare pure phase, without the presence of a pyrochlore impurity phase which degrades the dielectric properties. Depending on the processing conditions, the amount of pyrochlore phase varies.Considering the ternary diagram PbO-MgO-Nb2O5, different compositions have been prepared by a simple sol-gel method at room temperature using Pb(CH3COO)2, Mg(CH3COO)2, Nb(OC2H5)5 as precursors. After the heat treatment, the samples obtained were analyzed by XRD and EPMA with the purpose of studying the compositions formed.From the analysis of these results, it seems to be that the appearance of pyrochlore can be related to the reactivity of the MgO and/or the presence of other phases of the binary system PbO-Nb2O5. An excess of Pb and Mg is necessary for compositions to be formed near the PMN. The control of the amount of these two elements is very important because an excess of MgO would lead to rich compositions in Mg as a secondary phase. 相似文献
38.
Agüera A Pérez Estrada LA Ferrer I Thurman EM Malato S Fernández-Alba AR 《Journal of mass spectrometry : JMS》2005,40(7):908-915
Exact mass capabilities of time-of-flight (TOF) mass spectrometry along with other mass spectrometric techniques have been evaluated to elucidate a complete range of dichlofenac phototransformation products. Photolysis experiments with diclofenac in water under direct solar irradiation were performed to characterise the main phototransformation products generated and to determine their stability. Photolysis experiments were performed in both demineralised water and reconstructed standard freshwater. Samples were extracted before analysis by solid phase extraction (SPE) with Oasis HLB and MAX cartridges. Separation and identification of the transformation products were accomplished by the combined use of gas chromatography-mass spectrometry (GC/MS) and liquid chromatography coupled with time-of-flight mass spectrometry (LC/TOFMS). Both techniques provided complementary information that enabled the identification of 13 phototransformation products. Six of them were identified by GC/MS through the structural information provided by the full scan mass spectra obtained under electron impact (EI) ionisation and the confirmation of the molecular mass provided by positive chemical ionisation (PCI) analyses. Accurate mass measurements obtained by LC/TOFMS provided the elucidation of seven polar transformation products. The low mass error observed (<2 ppm) enabled the assignment of highly probable empirical formulas as well as identification of a process dimerisation route. The photoproducts identified demonstrated that photolysis of diclofenac occurs by two main routes. One is the consequence of the initial photocyclisation of diclofenac into carbazole derivatives. The other route goes through the initial decarboxilation of diclofenac and further oxidation of the alkyl-chain, which are typical photolytic process reactions. The main photoproduct identified was 8-chloro-9H-carbazole-1yl-acetic acid. 相似文献
39.
Several new methyl-substituted indenyl ferrocenes were prepared by metathesis reactions of the indenide (generated from the appropriate indene with BuLi) with ferrous chloride. The indenides used to prepare new ferrocenes were: 2-methyl-, 1,2-dimethyl-, 4,7-dimethyl-, 1,4,7-trimethyl-, and 1,3,4,7-tetramethyl-indenide. These indenyl ferrocenes, along with those prepared from indenide, 1-methylindenide, and 1,3-dimethylindenide, were then characterized by 1H and 13C NMR, UV/visible spectroscopy, cyclic voltammetry and mass spectrometry. The cyclic voltammetry showed an additive relationship between oxidation potential and the number of methyl groups which is also position-dependent, whereas the UV/visible spectra showed two absorptions essentially unaffected by methyl substitution. Additionally, bis(2-methylindenyl)iron(II) and bis(4,7-dimethylindenyl)iron(II) were characterized by X-ray crystallography. 相似文献
40.