全文获取类型
收费全文 | 469719篇 |
免费 | 3372篇 |
国内免费 | 1114篇 |
专业分类
化学 | 238237篇 |
晶体学 | 7437篇 |
力学 | 21657篇 |
综合类 | 17篇 |
数学 | 62999篇 |
物理学 | 143858篇 |
出版年
2020年 | 3430篇 |
2019年 | 3854篇 |
2018年 | 11887篇 |
2017年 | 12549篇 |
2016年 | 10486篇 |
2015年 | 4929篇 |
2014年 | 6969篇 |
2013年 | 17487篇 |
2012年 | 16114篇 |
2011年 | 25488篇 |
2010年 | 16705篇 |
2009年 | 16757篇 |
2008年 | 22796篇 |
2007年 | 25748篇 |
2006年 | 13450篇 |
2005年 | 17408篇 |
2004年 | 13588篇 |
2003年 | 12812篇 |
2002年 | 10839篇 |
2001年 | 11264篇 |
2000年 | 8866篇 |
1999年 | 6584篇 |
1998年 | 5432篇 |
1997年 | 5425篇 |
1996年 | 5213篇 |
1995年 | 4560篇 |
1994年 | 4518篇 |
1993年 | 4394篇 |
1992年 | 5118篇 |
1991年 | 5089篇 |
1990年 | 4946篇 |
1989年 | 4989篇 |
1988年 | 4933篇 |
1987年 | 4912篇 |
1986年 | 4682篇 |
1985年 | 6037篇 |
1984年 | 6216篇 |
1983年 | 4942篇 |
1982年 | 5269篇 |
1981年 | 5212篇 |
1980年 | 4836篇 |
1979年 | 5360篇 |
1978年 | 5488篇 |
1977年 | 5505篇 |
1976年 | 5397篇 |
1975年 | 4979篇 |
1974年 | 4918篇 |
1973年 | 5032篇 |
1972年 | 3403篇 |
1967年 | 3314篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
1.
ABSTRACTQM(UB3LYP)/MM(AMBER) calculations were performed for the locations of the transition structure (TS) of the oxygen–oxygen (O–O) bond formation in the S4 state of the oxygen-evolving complex (OEC) of photosystem II (PSII). The natural orbital (NO) analysis of the broken-symmetry (BS) solutions was also performed to elucidate the nature of the chemical bonds at TS on the basis of several chemical indices defined by the occupation numbers of NO. The computational results revealed a concerted bond switching (CBS) mechanism for the oxygen–oxygen bond formation coupled with the one-electron transfer (OET) for water oxidation in OEC of PSII. The orbital interaction between the σ-HOMO of the Mn(IV)4–O(5) bond and the π*-LUMO of the Mn(V)1=O(6) bond plays an important role for the concerted O–O bond formation for water oxidation in the CaMn4O6 cluster of OEC of PSII. One electron transfer (OET) from the π-HOMO of the Mn(V)1=O(6) bond to the σ*-LUMO of the Mn(IV)4–O(5) bond occurs for the formation of electron transfer diradical, where the generated anion radical [Mn(IV)4–O(5)]-? part is relaxed to the ?Mn(III)4?…?O(5)- structure and the cation radical [O(6)=Mn(V)1]+ ? part is relaxed to the +O(6)–Mn(IV)1? structure because of the charge-spin separation for the electron-and hole-doped Mn–oxo bonds. Therefore, the local spins are responsible for the one-electron reductions of Mn(IV)4->Mn(III)4 and Mn(V)1->Mn(IV)1. On the other hand, the O(5)- and O(6)+ sites generated undergo the O–O bond formation in the CaMn4O6 cluster. The Ca(II) ion in the cubane- skeleton of the CaMn4O6 cluster assists the above orbital interactions by the lowering of the orbital energy levels of π*-LUMO of Mn(V)1=O(6) and σ*-LUMO of Mn(IV)4–O(5), indicating an important role of its Lewis acidity. Present CBS mechanism for the O–O bond formation coupled with one electron reductions of the high-valent Mn ions is different from the conventional radical coupling (RC) and acid-base (AB) mechanisms for water oxidation in artificial and native photosynthesis systems. The proton-coupled electron transfer (PC-OET) mechanism for the O–O bond formation is also touched in relation to the CBS-OET mechanism. 相似文献
2.
3.
The structure, chemical composition, and magnetic properties of electrochemically deposited nanocrystalline Co-Ni-Fe films
were investigated using a number of techniques. A high saturation magnetic induction up to B
s
= 21 kG was attained. An enhancement of the saturation magnetization compared to the ideal anticipated one was revealed,
which correlated with the nonlinear behavior of the structural phase composition and lattice parameters with the change of
the composition.
The text was submitted by the authors in English. 相似文献
4.
Experimental data on the effect of thallium and sodium impurities on the lattice heat conductivity of PbTe at room temperature
are reported. Because the lattice of lead chalcogenides is strongly polarized near charged impurities, the effect of impurities
on the lattice heat conductivity depends substantially on their charge state. This property of the material has been used
to determine the charge state of the thallium impurity in PbTe. The results obtained argue for a model of quasi-local thallium-impurity
states which assumes low electron-correlation energy at an impurity center.
Fiz. Tverd. Tela (St. Petersburg) 40, 1206–1208 (July 1998) 相似文献
5.
The lidar equation for the vibrational backscattering of neodymium laser radiation and its harmonics by hydrogen molecules
is solved numerically. Inclined paths in the atmosphere are investigated with the aim of selecting the transmitter wavelength
for detecting the lowest concentrations of hydrogen.
Zh. Tekh. Fiz. 68, 20–22 (January 1998) 相似文献
6.
E. Jackiewicz M. Lukasiak M. Kopcewicz K. Szpila N. Bakun-Czubarow 《Hyperfine Interactions》1992,70(1-4):993-996
Terrestrial basalt rocks considered to be a good analogues of the Martian regolith were studied by using the Mössbauer spectroscopy and X-ray diffraction. The weathering of basalts was followed by the changes of the Fe2+/Fe3+ ratio. The basalt rock undergoes alteration from primary mineral composition (olivine+pyroxene+plagioclase) through smectite to kaolinite clay with oxides and hydroxides with the increase of the Fe2+/Fe3+ ratio. 相似文献
7.
NaY zeolite samples loaded with sodium metal by vapor phase deposition have been investigated using129Xe NMR spectroscopy. At low sodium concentration, the129Xe NMR spectrum showed three resonance lines which clearly indicate the existence of distinct domains in the zeolite sample. Such an observation suggests that the diffusion of the xenon atoms into each domain only occurs with respect to the NMR time scale (2.9 ms). As the sodium concentration increases, observation of a single broad line indicate a macroscopic homogenization of the system. The shift of this line is explained in part due to a paramagnetic interaction between the xenon atoms and the unpaired electrons of particles containing an odd number of sodium atoms. The linewidth is due to the distribution of the local magnetic fields partially averaged by the rapid motion of the xenon atoms and to the statistical distribution of the sodium particles in the supercage cavities. The paramagnetic interaction vanishes with the oxidation of the sample leading to a narrowing and a shift of the line to higher magnetic fields. 相似文献
8.
A. K. Lopatin 《Ukrainian Mathematical Journal》1997,49(1):51-74
We consider the method of normal forms, the Bogolyubov averaging method, and the method of asymptotic decomposition proposed by Yu. A. Mitropol’skii and the author of this paper. Under certain assumptions about group-theoretic properties of a system of zero approximation, the results obtained by the method of asymptotic decomposition coincide with the results obtained by the method of normal forms or the Bogolyubov averaging method. We develop a new algorithm of asymptotic decomposition by a part of the variables and its partial case — the algorithm of averaging on a compact Lie group. For the first time, it became possible to consider asymptotic expansions of solutions of differential equations on noncommutative compact groups. 相似文献
9.
Alloys of the systems Fe–Al (mixable over the whole concentration range) and Fe–Mg (insoluble with each other) were produced by implantation of Fe ions into Al and Mg, respectively. The implantation energy was 200 keV and the ion doses ranged from 1 × 1014 to 9 × 1017cm-2The obtained implantation profiles were determined by Auger electron spectroscopy depth profiling. Maximum iron concentrations reached were up to 60 at.% for implantation into Al and 94 at.% for implantation into Mg. Phase analysis of the implanted layers was performed by conversion electron Mössbauer spectroscopy and X‐ray diffraction. For implantation into Mg, two different kinds of Mössbauer spectra were obtained: at low doses paramagnetic doublets indicating at least two different iron sites and at high doses a dominant ferromagnetic six‐line‐pattern with a small paramagnetic fraction. The X‐ray diffraction pattern concluded that in the latter case a dilated αiron lattice is formed. For implantation into Al, the Mössbauer spectra were doublet structures very similar to those obtained at amorphous Fe–Al alloys produced by rapid quenching methods. They also indicated at least two different main iron environments. For the highest implanted sample a ferromagnetic six‐line‐pattern with magnetic field values close to those of Fe3Al appeared. 相似文献
10.
S. A. Gurevich T. A. Zaraiskaya S. G. Konnikov V. M. Mikushkin S. Yu. Nikonov A. A. Sitnikova S. E. Sysoev V. V. Khorenko V. V. Shnitov Yu. S. Gordeev 《Physics of the Solid State》1997,39(10):1691-1695
The concentration and chemical state of copper in the subsurface region of Cu/SiO2 composite films obtained by simultaneous magnetron sputtering from two sources (Cu and SiO2) are determined by x-ray photoelectron spectroscopy (XPS). It is established that copper in the as-grown film is primarily in the form of unoxidized atoms dispersed in a SiO2 matrix. Annealing of the film results in practically no oxidation, but about 70% of the copper atoms condense into metallic clusters with sizes below 10 Å in the subsurface region and about 50 Å in the bulk of the film. The changes in the binding energy of core electrons, and especially in the energies of Auger electrons, are so large in this situation that photoelectron and Auger spectroscopy are efficient methods for monitoring the chemical state of this composite material. 相似文献