全文获取类型
收费全文 | 12973篇 |
免费 | 2793篇 |
国内免费 | 1291篇 |
专业分类
化学 | 7683篇 |
晶体学 | 198篇 |
力学 | 75篇 |
综合类 | 64篇 |
数学 | 49篇 |
物理学 | 6832篇 |
综合类 | 2156篇 |
出版年
2024年 | 26篇 |
2023年 | 103篇 |
2022年 | 296篇 |
2021年 | 322篇 |
2020年 | 407篇 |
2019年 | 322篇 |
2018年 | 339篇 |
2017年 | 334篇 |
2016年 | 513篇 |
2015年 | 570篇 |
2014年 | 654篇 |
2013年 | 1117篇 |
2012年 | 770篇 |
2011年 | 825篇 |
2010年 | 672篇 |
2009年 | 753篇 |
2008年 | 729篇 |
2007年 | 923篇 |
2006年 | 897篇 |
2005年 | 737篇 |
2004年 | 625篇 |
2003年 | 633篇 |
2002年 | 559篇 |
2001年 | 541篇 |
2000年 | 470篇 |
1999年 | 394篇 |
1998年 | 382篇 |
1997年 | 326篇 |
1996年 | 269篇 |
1995年 | 246篇 |
1994年 | 224篇 |
1993年 | 173篇 |
1992年 | 158篇 |
1991年 | 117篇 |
1990年 | 134篇 |
1989年 | 110篇 |
1988年 | 97篇 |
1987年 | 64篇 |
1986年 | 56篇 |
1985年 | 31篇 |
1984年 | 34篇 |
1983年 | 10篇 |
1982年 | 14篇 |
1981年 | 20篇 |
1980年 | 15篇 |
1979年 | 8篇 |
1978年 | 12篇 |
1975年 | 6篇 |
1974年 | 3篇 |
1973年 | 8篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
171.
Toru Egawa Yukari Kachi Tsuguhide Takeshima Hiroshi Takeuchi Shigehiro Konaka 《Journal of Molecular Structure》2003,658(3):241-251
The molecular structure and conformation of carvone, a compound with a minty odor, were investigated by means of gas electron diffraction supported by theoretical calculations. Electron diffraction patterns were recorded by heating the nozzle up to 128 °C to obtain enough scattering intensity. The infrared spectrum was also measured by using an absorption cell with a path length of 10 m. The obtained molecular scattering intensities were analyzed with the aid of theoretical calculations and infrared spectroscopy. It was revealed that the experimental data are well reproduced by assuming that carvone consists of a mixture of three conformers that have the isopropenyl group in the equatorial position and mutually differ in the torsional angle around the single bond connecting the ring and the isopropenyl group. It was also found that the puckering amplitude of the ring of carvone is close to those of menthol and isomenthol, a minty compound and its nonminty isomer. The determined structural parameters (rg and ∠α) of the most abundant conformer of carvone are as follows: 〈r(C-C)〉=1.520(3) Å; 〈r(CC)〉=1.360(5) Å; r(CO)=1.225(5) Å; 〈r(C-H)〉=1.104(4)Å; 〈∠CC-C〉=121.1(5)°; 〈∠C-C-C〉=110.4(5)°; ∠C-CO-C=117.1(14)°; 〈∠C-C-H〉=111.1(13)°. Angle brackets denote average values and parenthesized values are the estimated limits of error (3σ) referring to the last significant digit. 相似文献
172.
《Surface and interface analysis : SIA》2003,35(3):327-328
This International Standard specifies a method for calibrating the kinetic energy scales of Auger electron spectrometers for elemental and chemical‐state analysis at surfaces. It is only applicable to instruments that incorporate an ion gun for sputter cleaning. This International Standard further specifies a method to establish a calibration schedule, to test for the kinetic energy scale linearity at one intermediate energy, to confirm the uncertainty of the scale calibration at one low and one high kinetic energy value, to correct for small drifts of that scale and to define the expanded uncertainty of the calibration of the kinetic energy scale for a confidence level of 95%. This uncertainty includes contributions for behaviours observed in interlaboratory studies but does not cover all of the defects that could occur. This International Standard is not applicable to instruments with kinetic energy scale errors that are significantly non‐linear with energy, to instruments operated at relative resolutions poorer than 0.2% in the constant ΔE/E mode or poorer than 1.5 eV in the constant ΔE mode, to instruments requiring tolerance limits of ±0.05 eV or less or to instruments equipped with an electron gun that cannot be operated in the energy range 5–10 keV. This standard does not provide a full calibration check, which would confirm the energy measured at each addressable point on the energy scale and should be performed according to the manufacturer's recommended procedures. Crown Copyright © 2003. Published by John Wiley & Sons, Ltd. 相似文献
173.
A. V. Belyakov A. V. Golubinskii L. V. Vilkov V. I. Shiryaev E. M. Styopina E. A. Kovalyova V. S. Nikitin 《Russian Chemical Bulletin》1993,42(2):346-349
The molecular structure of gaseous Br2Sn(CH2SiMe2)2O was studied by electron diffraction. The six-membered ring has a chair conformation whereas the entire molecule possessesC
s
symmetry. The existence of a boat conformer cannot be completely excluded. The results of theoretical calculations for a twisted-boat conformation are at variance with the experimental data. Steric strain caused by mutual repulsion of the two axial methyl groups is reduced to the tilt of the Me2Si fragments in opposite directions. This results in an increase (up to 26°C) in the angle formed by the bisector of the CM-Si-CM angle with the CcSiO plane. The main geometrical parameters are as follows:r
g (Å): Si-O 1.708(20); Si-CM 1.862(20); Si-Cc 1.882(9); Sn-C 2.108(26); Sn-Br 2.456(3); C-H 1.099(30); (degr.): C-Sn-C 105(2); Br-Sn-Br 107.9(1.2); Si-O-Si 129.6(3); CM-Si-CM 112; Si-C-H 113 (fixed value in accordance with experiment); Cc-Si-O 107(2); Sn-C-Si 109(2); torsion angles: (Si-C) 52(2); (Si-O) 62(1); (Cc-Sn) 54(1). The average amplitudes were fixed at the values calculated from the force field. Structural parameters of molecules with similar structures were analyzed and compared.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 384–387, February, 1993. 相似文献
174.
175.
C. AutretC. Martin A. MaignanM. Hervieu B. RaveauG. André F. Bourée 《Journal of solid state chemistry》2002,165(1):65-73
The Ho0.5Sr0.5MnO3 perovskite, synthesized in air, has been studied by combining neutron powder and electron diffraction techniques. The Pnma-type structure exhibits a strong tilting of the MnO6 octahedra. This octahedra tilting and microtwinning involve a complex strained structure. No structural transition is observed down to 1.4 K, but short-range A-type antiferromagnetism running over only a few perovskite subcells is evidenced below ≈90 K. The different behavior of this perovskite compared to other Ln0.5Sr0.5MnO3 perovskites is discussed in terms of A-site cationic mismatch. 相似文献
176.
自由基链式亲核取代反应(S_(RN)1)的进展 总被引:1,自引:0,他引:1
本文评述了自由基链式亲核取代反应的最近进展。内容包括:脂肪族化合物和芳香族化合物按S_(RN)l进行的反应及其机理。 相似文献
177.
178.
179.
Excitation energies of 123 polycyclic aromatic hydrocarbons were calculated by incorporating the improved method of new-γ for the two-center electron repulsion integral into two semiempirical molecular orbital methods (CNDO/S and INDO/S). This variable method well reproduced experimental excitation energies of them. The average error of the improvement is about 0.162 (CNDO/S) or 0.237 eV (INDO/S) though the average error without the improvement is about 0.541 (CNDO/S) or 0.536 eV (INDO/S). The improvement was useful for the calculations of other organic compounds including hetero atoms, such as organic dye. 相似文献
180.
Kinetics of chemiluminescence reactions of 2-methyl-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one (1c, Cypridina luciferin analogue) and substituent effects of the 6-aryl group of derivatives 1 strongly suggest that the rate-determining step is a single electron transfer from an anion derived from 1 to a triplet molecular oxygen (O2) in the oxygenation process. 相似文献