全文获取类型
收费全文 | 25506篇 |
免费 | 2344篇 |
国内免费 | 2258篇 |
专业分类
化学 | 18780篇 |
晶体学 | 325篇 |
力学 | 708篇 |
综合类 | 104篇 |
数学 | 1363篇 |
物理学 | 8828篇 |
出版年
2023年 | 158篇 |
2022年 | 322篇 |
2021年 | 419篇 |
2020年 | 539篇 |
2019年 | 583篇 |
2018年 | 472篇 |
2017年 | 580篇 |
2016年 | 817篇 |
2015年 | 893篇 |
2014年 | 922篇 |
2013年 | 2132篇 |
2012年 | 1205篇 |
2011年 | 1291篇 |
2010年 | 1105篇 |
2009年 | 1427篇 |
2008年 | 1534篇 |
2007年 | 1641篇 |
2006年 | 1539篇 |
2005年 | 1358篇 |
2004年 | 1294篇 |
2003年 | 1245篇 |
2002年 | 1060篇 |
2001年 | 830篇 |
2000年 | 857篇 |
1999年 | 759篇 |
1998年 | 677篇 |
1997年 | 586篇 |
1996年 | 575篇 |
1995年 | 549篇 |
1994年 | 443篇 |
1993年 | 354篇 |
1992年 | 435篇 |
1991年 | 255篇 |
1990年 | 188篇 |
1989年 | 181篇 |
1988年 | 167篇 |
1987年 | 120篇 |
1986年 | 94篇 |
1985年 | 79篇 |
1984年 | 77篇 |
1983年 | 46篇 |
1982年 | 59篇 |
1981年 | 32篇 |
1980年 | 36篇 |
1979年 | 40篇 |
1978年 | 23篇 |
1977年 | 16篇 |
1976年 | 23篇 |
1974年 | 15篇 |
1973年 | 15篇 |
排序方式: 共有10000条查询结果,搜索用时 20 毫秒
91.
Jnos Szanyi Ja Hun Kwak Sarah Burton Jose A. Rodriguez Charles H.F. Peden 《Journal of Electron Spectroscopy and Related Phenomena》2006,150(2-3):164-170
Adsorbed ionic NOx species formed upon the interaction of NO2 with dehydrated or hydrated Na- and Ba-Y, FAU zeolites were characterized using FT-IR/TPD, solid state NMR, and XANES techniques. NO2 disproportionates on both dehydrated catalyst materials forming NO+ and NO3− species. These ionic species are stabilized by their interactions with the negatively charged zeolite framework and the charge compensating cations (Na+ and Ba2+), respectively. Although the nature of the adsorbed NOx species formed on the two catalysts is similar, their thermal stabilities are strongly dependent on the charge compensating cations. In the presence of water in the channels of these zeolite materials new paths open for reactions between NO+ and H2O, and NO2 and H2O, resulting in significant changes in the adsorbed ionic species observed. These combined spectroscopic investigations afforded the understanding of the interactions between water and NO2 on these zeolite catalysts. 相似文献
92.
High-resolution Fourier transform spectra of CH3OH have been investigated in the infrared region from 930 to 1450 cm−1 in order to map the torsion-rotation energy manifolds associated with the ν7 in-plane CH3 rock, the ν11 out-of-plane CH3 rock, and the ν6 OH bend. Upper-state term values have been determined from the assigned spectral subbands, and have been fitted to power-series expansions to obtain substate origins and effective B-values for the three modes. The substate origins have been grouped into related families according to systematic trends observed in the torsion-vibration energy map, but there are substantial differences from the traditional torsional patterns. There appears to be significant torsion-mediated spectral mixing, and a variety of “forbidden” torsional combination subbands with |Δυt|>1 have been observed, where υt denotes the torsional quantum number (equivalent to υ12). For example, coupling of the (υ6,υt)=(1,0) OH bend to nearby torsionally excited (υ7,υt)=(1,1) CH3-rock and (υ8,υt)=(1,1) CO-stretch states introduces (υ6,υt)=(1,0)←(0,1) subbands into the spectrum and makes the ν7+ν12−ν12 torsional hot band stronger than the ν7 fundamental. The results suggest a picture of strong coupling among the OH-bending, CH3-rocking, and CO-stretching modes that significantly modifies the traditional energy structure and raises interesting and provocative questions about the torsion-vibration identity of a number of the observed states. 相似文献
93.
P.S Erdman M Fajardo K.M Sando W.C Stwalley 《Journal of Quantitative Spectroscopy & Radiative Transfer》2004,88(4):447-481
Experimental results are reported for a unique spectroscopic device called the Plasma Spectroscopy Cell. Optical absorption of lithium metal vapor was observed at high density and temperature. Absorption spectra are analyzed using theoretical calculations of absorption cross sections for lithium-helium interactions, and singlet and triplet state transitions of diatomic lithium in the visible spectral range. This is believed to be the most complex example yet calculated in which absolute bound-bound, bound-free, free-bound, and free-free contributions for all possible optically allowed transitions are all included, in quite respectable agreement with experiment. 相似文献
94.
The signals of a single-pulse echo (SE) generated on nonresonant excitation of an inhomogeneously broadened two-level system by a radio-frequency pulse (RFP), against the background of which a magnetic video pulse (MVP) of certain length has been switched on, have been described analytically. It is established that under the conditions of such excitation several SE signals are formed whose generation moments are determined by the duration and amplitudes of the RFP and MVP. The amplitudes of some of these signals depend on the Rabi frequency according to a quadratic law, and the amplitudes of others depend on this frequency according to a biquadratic law. It has been established that the mechanism underlying the appearance of these signals is associated with zero beats arising as a result of superposition of the magnetization fluctuations at variable frequencies and at a frequency of detuning from resonance. It is shown that in the limiting case, where the RFP duration considerably exceeds the duration of the MVP or is comparable with it, the number of SE signals decreases to two. Theoretical results on the formation of SE and the dependence of the amplitude of these signals on the MVP amplitude agree with the experimental data on NMR pulsed signals in ferromagnetic materials. 相似文献
95.
1D-nanostructural zinc oxide (ZnO) with different shapes have been synthesized on p-type Si(1 0 0) and glass substrates via vapor phase growth by heating pure zinc powder at temperatures between 480 and 570 °C. The different ZnO nanostructures depend on the substrates and the growth temperatures. Scanning electron microscopy and X-ray diffraction revealed that a well-aligned nanowires array, which are vertical to the substrate of Si(1 0 0) with 18 sides on their heads, but six sides on their stems, has been formed at 480 °C. Raman study on the ZnO nanostructures shows that the coupling strength between electron and phonon determined by the ratio of the second- to the first-order Raman scattering cross-sections declines with decreasing diameter of the nanowires. However, a little changes of the coupling strength in terms of the width of the nanobelts have been observed. 相似文献
96.
明确从地胆草中分离得到的两对牦牛儿内酯型的立体异构体即地胆草种内酯(scabertopin)、异地胆草种内酯(isoscabertopin)、异去氧地胆草内酯(isodeoxyelephantopin)和去氧地胆草内酯(deoxyelephantopin)的C-2相对构型;方法 NOESY技术,并结合这4个化合物的1H NMR,13C NMR,HMQC谱;结果 两对立体异构体的NOESY谱有明显差异;结论 通过分析NOESY谱,找寻H-1相关信息,若发现H-1与H-8,H-9β和14-CH3有NOE相关,可以判断化合物的C-2为α构型,若H-1与H-5,H-7,H-3α及H-9α之间有NOE相关,则化合物的C-2为β构型. 相似文献
97.
Maculalactones A, B and C from the marine cyanobacterium Kyrtuthrix maculans are amongst the only compounds based on the tribenzylbutyrolactone skeleton known in nature and (+) maculalactone A from the natural source possesses significant biological activity against various marine herbivores and marine settlers. We now report a concise synthesis of racemic maculalactone A in five steps from inexpensive starting materials. Maculalactones B and C were synthesized by a minor modification to this procedure, and the synthetic design also permitted an asymmetric synthesis of maculalactone A to be achieved in around 85% ee. The (+) and (−) enantiomers of maculalactone A were assigned, respectively, to the S and R configurations on the basis of the chiral selectivity expected for catecholborane reduction of an unsymmetrical ketone in the presence of Corey's oxazoborolidine catalyst. Surprisingly, it appeared that natural (+) maculalactone A was biosynthesized in K. maculans in a partially racemic form, comprising ca. 90-95% of the (S) enantiomer and 5-10% of its (R) enantiomer. Coincidentally therefore, the percentage enantiomeric excess of the product obtained from asymmetric synthesis almost exactly matched that found in nature. 相似文献
98.
99.
The vibronic spectra of charge transfer excitons (CTE) in a molecular one-component or alternatingly ordered two-component chain are treated in the framework of a dynamic approach (neglecting thermal excitations of the intramolecular vibrations). The model introduces two mechanisms of coupling between CTEs and vibrational quanta: (1) shift of the equilibrium positions of the nuclei in the ionized donor or acceptor; (2) change of the vibrational frequency in the ionized molecule. This model allows to generalize the simple CTE Hamiltonian and the vibronic Hamiltonian of Frenkel excitons. The linear optical susceptibility is calculated in the vibronic region (one CTE and one vibrational quantum). The double splitting of vibronics of CTEs was analyzed: (1) the splitting connected with the location of the intramolecular vibration on the donors or on the acceptors; (2) the splitting connected with the symmetry of the vibronic spectra (in the degenerate case). The general structure of the vibronic spectra of CTEs is established. It contains structureless absorption lines, which correspond to two-particle bands (the phonon is excited on a neutral molecule neighboring the donor or the acceptor) and Lorentz-type lines of one-particle states, which correspond to the bound propagation of the CTE and the phonon. 相似文献
100.
It has been shown that the kinetics of intramolecular processes and time-resolved spectra with allowance for the quantum beats of the resonant states of isomers or isolated subsystems of levels of one isomeric form can be described with the use of a molecular model interpreting the effect of beats as a nonradiative transition. We have obtained an expression for the nonradiative transition probability, which is directly proportional to the beat frequency and depends oscillatorily on time, thus modeling the effect of beats. The parameter of the molecular system model is the beat frequency directly related to the parameter characterizing the intramolecular interisomeric interactions (the corresponding nondiagonal element of the energy matrix) rather than the value of the nonradiative transition probability. The character of the change in the level populations and, accordingly, in the band intensities in the spectra in the proposed model is in good agreement with the experiment, including the fine structure of the time dependences — oscillations of the line intensities. In analyzing the temporal experiment with a high resolution, it is necessary to take into account the instrument function leading to quantitative and qualitative changes in the time dependences. The traditional model of nonradiative transitions with a constant probability value has a very limited range of applicability — very high beat frequencies compared to the probability of optical transitions. 相似文献