全文获取类型
收费全文 | 4854篇 |
免费 | 1240篇 |
国内免费 | 632篇 |
专业分类
化学 | 3637篇 |
晶体学 | 40篇 |
力学 | 217篇 |
综合类 | 36篇 |
数学 | 524篇 |
物理学 | 2272篇 |
出版年
2024年 | 16篇 |
2023年 | 76篇 |
2022年 | 176篇 |
2021年 | 208篇 |
2020年 | 274篇 |
2019年 | 207篇 |
2018年 | 167篇 |
2017年 | 201篇 |
2016年 | 275篇 |
2015年 | 256篇 |
2014年 | 370篇 |
2013年 | 416篇 |
2012年 | 353篇 |
2011年 | 363篇 |
2010年 | 312篇 |
2009年 | 311篇 |
2008年 | 322篇 |
2007年 | 283篇 |
2006年 | 281篇 |
2005年 | 232篇 |
2004年 | 248篇 |
2003年 | 195篇 |
2002年 | 150篇 |
2001年 | 126篇 |
2000年 | 115篇 |
1999年 | 100篇 |
1998年 | 106篇 |
1997年 | 88篇 |
1996年 | 85篇 |
1995年 | 60篇 |
1994年 | 61篇 |
1993年 | 42篇 |
1992年 | 48篇 |
1991年 | 32篇 |
1990年 | 26篇 |
1989年 | 17篇 |
1988年 | 19篇 |
1987年 | 13篇 |
1986年 | 20篇 |
1985年 | 7篇 |
1984年 | 8篇 |
1982年 | 12篇 |
1981年 | 7篇 |
1980年 | 11篇 |
1979年 | 9篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1975年 | 2篇 |
1974年 | 4篇 |
1973年 | 3篇 |
排序方式: 共有6726条查询结果,搜索用时 15 毫秒
61.
A novel asymmetric, edge-sharing bioctahedral complex with formamidinato ligands (
2-DAniF)Mo(-DAniF)2(-O,Cl)MoCl2, 1, (DAniF=N,N-di-p-anisylformamidinate) has been isolated as a byproduct from the preparation of the dimolybdenum(II,III) compound Mo2(DAniF)3Cl2. An X-ray crystallographic study shows that the structure consists of edge-sharing bioctahedra, with the shared edge defined by the vector joining the: -O and -Cl ligands. Compound 1 is best formulated as a mixed-valent MoIIIMoV compound, the Mo(V) ion being that with the two terminal Cl– ligands. The cyclic voltammogram of 1 shows a reversible reduction at –0.472 V and a reversible oxidation at 1.028 V vs. the Ag/AgCl reference electrode, while the absorption spectrum of 1 reveals an intense low energy absorption at 523 nm (
max=12 500) which is attributed to an intervalence charge transfer transition. Crystallographic data for 1 are as follows: a=13.387(1) Å, b=15.500(2) Å, c=21.855(2) Å, =98.786(2)°, V=4481.8(8) Å3, P21/c, R1 (wR2)=0.082 (0.177). 相似文献
62.
F López Arbeloa J Ba?uelos Prieto V Martínez Martínez T Arbeloa López I López Arbeloa 《Chemphyschem》2004,5(11):1762-1771
Absorption and fluorescence (steady-state and time-correlated) techniques are used to study the photophysical characteristics of the pyrromethene 650 (PM650) dye. The presence of the cyano group at the 8 position considerably shifts the absorption and fluorescence bands to lower energies with respect to other related pyrromethene dyes; this is attributed to the strong electron-acceptor character of the cyano group, as is theoretically confirmed by quantum mechanical methods. The fluorescence properties of PM650 are intensively solvent-dependent. The fluorescence band is shifted to lower energies in polar/protic solutions, and the evolution of the corresponding wavelength with the solvent is analysed by a multicomponent linear regression. The fluorescence quantum yield and the lifetime strongly decrease in polar/protic solvents, which can be ascribed to an extra nonradiative deactivation, via an intramolecular charge-transfer state (ICT state), favoured in polar media. 相似文献
63.
M.E. Kletskii A.A. Millov A.V. Metelitsa M.I. Knyazhansky 《Journal of photochemistry and photobiology. A, Chemistry》1997,110(3):857-270
The mechanism of light-induced transformation in the salicylideneaniline molecule was studied by semiempirical PM3 calculations. The structures and energies of the minima and saddle points (transition states) on the S0, S1 and T1 potential energy hypersurfaces (PESs) were obtained, together with the gradient lines on the PESs. The structure-energy scheme was compared with the experimental findings. According to the results obtained, the following principle processes are observed: fast S1 excited state intramolecular proton transfer (ESIPT), followed by typical ESIPT fluorescence; the formation of two S1 twisted intramolecular charge transfer (TICT) structures which quench the ESIPT fluorescence; the diabatic formation of two ground state metastable coloured “post-TICT” structures responsible for photochromism. 相似文献
64.
Summary Electrophoretic mobility measurements in the pH 2‐10 range are described for several commercial HPLC silica microparticles
and a laboratory-produced product. The content of metal impurities for the silicas was also determined by AAS. An acidic/hydrothermal
treatment was used to generate a more homogenous surface for some of the silicas. The zero points of charge (zpc) for both
a native and a treated silica plus several commercial HPLC silicas were compared. The electrophoretic mobility method may
be useful in predicting the utility of certain types of silica supports for chromatographic separations. 相似文献
65.
Effect of solution chemistry on the surface charge of polymeric reverse osmosis and nanofiltration membranes 总被引:1,自引:0,他引:1
A streaming potential analyzer has been used to investigate the effect of solution chemistry on the surface charge of four commercial reverse osmosis and nanofiltration membranes. Zeta potentials of these membranes were analyzed for aqueous solutions of various chemical compositions over a pH range of 2 to 9. In the presence of an indifferent electrolyte (NaCl), the isoelectric points of these membranes range from 3.0 to 5.2. The curves of zeta potential versus solution pH for all membranes display a shape characteristic of amphoteric surfaces with acidic and basic functional groups. Results with salts containing divalent ions (CaCl2, Na2SO4, and MgSO4) indicate that divalent cations more readily adsorb to the membrane surface than divalent anions, especially in the higher pH range. Three sources of humic acid, Suwannee River humic acid, peat humic acid, and Aldrich humic acid, were used to investigate the effect of dissolved natural organic matter on membrane surface charge. Other solution chemistries involved in this investigation include an anionic surfactant (sodium dodecyl sulfate) and a cationic surfactant (dodecyltrimethylammonium bromide). Results show that humic substances and surfactants readily adsorb to the membrane surface and markedly influence the membrane surface charge. 相似文献
66.
The new layered ternary compound Nb3GexTe6 (x ? 0.90) was prepared by direct combination of the elements taken in the stoichiometric proportions 3 : 1 : 6, heated at 1 000 °C for 10 days in silica tubes and quenched to room temperature. The phase crystallizes in the orthorhombic symmetry, space group Pnma (#62), with the following single crystal refined parameters: a = 643.18(5) pm, b = 1391.98(11)pm and c = 1 154.07(5) pm, with Z = 4. The structure was refined to an R of 3.4% (Rw = 4.6%), with 1969 independent reflexions and 49 parameters. The structure is based on the close stacking of trigonal prismatic (TP) slabs in the AA/BB mode. The slabs can be seen as built up from face sharing biprisms, which are filled either by one or by two niobium cations situated in the middle of the trigonal prisms. The germanium is located in the middle of the common face of two prisms, leading to a rather unusual anionic square coordination. The refinements showed that this latter cation does not fill completely its square site. No cation was found in the van der Waals gap between the slabs. The mean dGe? Te distance (276.5 pm) is in agreement with GeII cations, while some Te …? Te distances (from 333.84 to 361.65pm) are too short for anions in a simple contact. These bonding distances, already mentionned in some MTe2 compounds, are to be ascribed to charge transfer in the structure, with a partial oxidation state for the tellurium anions. Short Nb? Nb and Nb? Ge distances (292.0 and 281.3 pm, respectively) imply intercationic bonding within the slabs. 相似文献
67.
68.
69.
The interaction energy of a molecule M with a point-like charge q can be partitioned into simpler contributions, two of which can be expressed in terms of the charge distribution M of the sole M. The first term, qV(r), represents the interaction of q with the undistorted charge
M
0
of M while the second q
2
P(r) gives the additional contributions due to the polarization of
M
0
under the influence of the charge q placed at the point r. In this paper we investigate the possibility of getting an inexpensive and sufficiently accurate analytical representation of P(r) over the whole space outside the van der Waals volume of M. 相似文献
70.