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881.
F. Meyer J. Dupré C. Meyer C. Lambeau M. De Vleeschouwer J. -G. Lahaye A. Fayt 《International Journal of Infrared and Millimeter Waves》1982,3(1):83-95
The 5 band of methylacetylene has been studied simultaneously by means of CO2 Laser Stark spectroscopy and high resolution infrared absorption spectroscopy (0.012 cm–1). The primary aim of this work was to assign all the Stark coïncidences. Effective vibration-rotation parameters and the dipole moment of the v5=1 state have been determined. 相似文献
882.
The structure of 2-nitroethanal has been studied at the MP2/6-31G* level in the gas phase and in acetonitrile using a continuum model to represent the electrostatic solute-solvent interactions. The relative energies of the two stable conformations obtained are quite dependent on the media. Indeed, our computations predict a change of the most stable conformation from gas to polar solvent. These results are in agreement with experimental data for the axial/equatorial conformational equilibrium of 2-nitrocyclohexanone. 相似文献
883.
The molecular structure and absorption spectra of monothio- and dithio-naphthalimides were compared to their naphthalimide analogues using AM1, PM3 and ZINDO/S semiempirical quantum chemical methods. The substitution of the 4R-naphthalimide oxygen atoms by sulphur atoms resulted in a red-shift of the absorption spectra by Δλmax60-65 and 100-140 nm, respectively. The thionated naphthalimide derivatives do not show observable fluorescence due to intersystem crossing to the triplet -states localised at the CS groups. The -absorption bands of monothioimides are located at 525-580 nm (ε=60-80) and those for dithioimides at 535-560 nm (ε=140-390) and 628-686 nm (ε=34-68). None of these transitions are solvent sensitive. The -transitions of N-phenylthioimides have also a small contribution from -states due to a partial conjugation between CS group and π-electronic system of the N-phenyl ring. As a result, the bands of aromatic substituted N-phenylthioimides are red-shifted as compared to those of the aliphatic N-methyl-thioimides. 相似文献
884.
Yu. I. Aristov G. Di Marco M. M. Tokarev V. N. Parmon 《Reaction Kinetics and Catalysis Letters》1997,61(1):147-154
In this communication we present a low-temperature “solidification-melting” phase diagram for CaCl2/H2O solutions confined in KSK and KSM silica gels. At salt concentrations of 0–48 wt. %, the diagram has been found to lie below
the diagram reported for the bulk system by 15–30°C. It shows a depression of the solution melting point due to its confinment
to the pores. Several other peculiarities of melting and solidification in this system are also reported and discussed. Beside
fundamental interest, the data obtained could be of importance in many commercial areas such as refrigeration, accumulation
of low temperature heat, frost prevention in building materials,etc. 相似文献
885.
Jun Li 《Journal of Cluster Science》2002,13(1):137-163
The electronic structures and bonding of isopoly oxometalates M6O19
2– (M=Cr, Mo, W) have been investigated by using ab initio and relativistic density functional methods. We have discussed the role of the central oxygen atom and the (d-p) conjugation interactions between the metal and bridging oxygen atoms. It is found that there exist 12 three-centered two-electron (d-p-d) bonds for the three M4(-O)4 planar rings in M6O19
2– ions and these hexametalates are considered to have quasi-aromaticity. The (d-p) conjugation effects play essential role in stabilizing these cluster compounds, and the reduced (d-p) conjugation effects account for the instability of the isopoly oxochromate ion, Cr6O19
2–. The vibrational spectra and electronic spectra of M6O19
2– ions are evaluated and assigned theoretically and the calculated spectra are in fairly good agreement with the measured experimental results. 相似文献
886.
K. Yu. Chegaev A. N. Kravchenko O. V. Lebedev Yu. A. Strelenko P. A. Belyakov 《Chemistry of Heterocyclic Compounds》2002,38(10):1250-1252
N-Trimethylsilyl derivatives of 2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-diones have been prepared for the first time and the electrophilic substitution reaction of the trimethylsilyl group has been studied. 相似文献
887.
The 57Fe Mössbauer effect in [Fe(pythiaz)2] (BF4)2 (I) and [Fe(pythiaz)2] (C&O4)2 (II) has been studied between 298 and 4.2°K (pythiaz = 2,4-bis(2-pyridyl)thiazole). At 298°K compound I shows a doublet with ΔEQ(5T2) = 1.29 mm sec?1 and δ1S(5T2) = +0.93 mm sec?1 characteristic of a 5T2 ground state. At 236°K, a second doublet, typical for a 1A1 ground state appears. The transition 5T2 å 1A1 progresses as the temperature is lowered but levels off below ≈ 120°K. At 4.2°K, 59% of the intensity is due to the 1A1 state, and ΔEQ(1A1) = 1.59 mm sec?1 and δ1S(1A1) = +0.26 mm sec?1. In an applied magnetic field, Vzz(1A1) < 0 has been determined Similar results have been obtained with compound II.Debye-Waller factors f5T2 and f1A1. were determined from the Mössbauer spectra under the assumption of Curie-Weiss dependence of the magnetism for the 5T2 and constant μeff for the 1A1 ground state. The resulting temperature dependence of f1A1 is highly unusual thus suggesting complicated magnetic behaviour of both ground states in the transition region. Two mechanisms for the nature of the transition are discussed, a “spin-flip” mechanism being the physically more reasonable one. The assumption of a simple Boltzmann distribution (“spin equilibrium”) may be ruled out for the solid but could be encountered in solutions. 相似文献
888.
苯并菲盘状液晶的合成、亲氟效应及分子对称性对介晶性的影响 总被引:3,自引:0,他引:3
New symmetrical and asymmetrical triphenylene-containing discotic liquid crystals with two different peripheral alkyl chains, known as sym-TP(OC6H13)3(OR)3 and asym-TP(OC6H13)3(OR)3, were synthesized. Their thermotropic liquid crystal properties were investigated through polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analyses. The asyrranetdcal discogens are 2,6,11-rialkoxy-3,7,10-trihexyloxytriphenylenes, with the alkyl chain carbon numbers varying from 3-10, 12, and 14, while the symmetrical compounds are 2,6,10-trialkyloxy-3,7,11-trihexyloxytriphenylene. Two fluoroalkoxy substituted triphenylene discogens, 2,6,10-td(4,4,4-trifluorobutoxy)-3,7,11-trihexyloxytriphenylene and its asymmetrical isomer 2,6,11-tri(4,4,4-trifluorobutoxy)-3,7,10-trihexyloxytdphenylene were prepared. These two compounds show higher melting and clearing points than their alkoxy analogs, which implies that fluorophilic effect exists in the formation and stabilization of discotic columnar mesophase. The triphenylene derivatives TP(OC6H13)3(OR)3 with two different peripheral chains, symmetrically or asymmetrically attached on triphenylene cores, have lower melting points and clearing points than those of the higher symmetrical compounds TP(OR)6 with the same total chain carbon numbers. The mixed-chain-triphenylenes with longer alkoxy chains (n=9,10,12,14) show columnarmesophase at room temperature. 相似文献
889.
The anomeric effect has been studied for a variety of compounds using the MM4 force field, and also using MP2/6-311++G(2d,2p) ab initio calculations and experimental data for reference purposes. Geometries and energies, including conformational, rotational barriers, and heats of formation were examined. Overall, the agreement of MM4 with the experimental and ab initio data is good, and significantly better than the agreement obtained with the MM3 force field. The anomeric effect is represented in MM4 by various explicit terms in the force constant matrix. The bond length changes are accounted for with torsion-stretch elements. The angle changes are accounted for with torsion-bend elements. The energies are taken into account with a number of torsional terms in the usual way. A torsion-torsion interaction is also of some importance. With all of these elements included in the calculation, the MM4 results now appear to be adequately accurate. The heats of formation were examined for a total of 12 anomeric compounds, and the experimental values were fit by MM4 with an RMS error of 0.42 kcal/mol. 相似文献
890.
ZHANG Gai LIANG Yong-Qing ZHANG Rong-Lan ZHANG Wei-Hai ZHAO Jian-She GUO Zhi-An 《结构化学》2005,24(7):783-789
A new quinazolinone compound 2,3-dihydro-2-(2-hydroxyphenyl)-3-phenylquinazolin-4(IH)-one 3 ([C2oH16O2N2]-C2H5OH, Mr = 362.42) and compound 2-(2-hydroxybenzylidene-amino)-N-phenyl-benzamide 2 (C2oH16O2N2, Mr = 316.34) were prepared from a precursor of 2-amino-N-phenyl-benzamide 1 (C13H12ON2, Mr = 212.25). Compound 3 was characterized by single-crystal X-ray diffraction analysis. The crystal belongs to orthorhombic,space group Pbca with a = 1.2889(11), b = 1.6170(14), c = 1.7729(15) nm, V= 3.695(6) nm^3, Z= 8, F(000) = 1536, Mr = 362.42, Dc = 1.303 g/cm^3, μ(MoKa) = 0.087 mm^-1, R = 0.0447 and wR= 0.0879. The crystal structure analysis indicates that the title compound has a two-dimensional network structure formed by hydrogen bonds and electrostatic interactions. 相似文献