全文获取类型
收费全文 | 356篇 |
免费 | 10篇 |
专业分类
化学 | 283篇 |
晶体学 | 6篇 |
力学 | 9篇 |
数学 | 15篇 |
物理学 | 53篇 |
出版年
2023年 | 3篇 |
2022年 | 2篇 |
2021年 | 3篇 |
2020年 | 7篇 |
2019年 | 7篇 |
2018年 | 3篇 |
2016年 | 13篇 |
2015年 | 2篇 |
2014年 | 8篇 |
2013年 | 15篇 |
2012年 | 26篇 |
2011年 | 15篇 |
2010年 | 9篇 |
2009年 | 15篇 |
2008年 | 28篇 |
2007年 | 15篇 |
2006年 | 17篇 |
2005年 | 23篇 |
2004年 | 18篇 |
2003年 | 16篇 |
2002年 | 18篇 |
2001年 | 4篇 |
1999年 | 4篇 |
1996年 | 1篇 |
1995年 | 8篇 |
1994年 | 6篇 |
1993年 | 7篇 |
1992年 | 5篇 |
1991年 | 7篇 |
1990年 | 1篇 |
1989年 | 4篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 4篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1980年 | 4篇 |
1979年 | 1篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1967年 | 10篇 |
1965年 | 1篇 |
1935年 | 1篇 |
排序方式: 共有366条查询结果,搜索用时 15 毫秒
1.
The rate constants k1 for the reaction of CF3CF2CF2CF2CF2CHF2 with OH radicals were determined by using both absolute and relative rate methods. The absolute rate constants were measured at 250–430 K using the flash photolysis–laser‐induced fluorescence (FP‐LIF) technique and the laser photolysis–laser‐induced fluorescence (LP‐LIF) technique to monitor the OH radical concentration. The relative rate constants were measured at 253–328 K in an 11.5‐dm3 reaction chamber with either CHF2Cl or CH2FCF3 as a reference compound. OH radicals were produced by UV photolysis of an O3–H2O–He mixture at an initial pressure of 200 Torr. Ozone was continuously introduced into the reaction chamber during the UV irradiation. The k1 (298 K) values determined by the absolute method were (1.69 ± 0.07) × 10?15 cm3 molecule?1 s?1 (FP‐LIF method) and (1.72 ± 0.07) × 10?15 cm3 molecule?1 s?1 (LP‐LIF method), whereas the K1 (298 K) values determined by the relative method were (1.87 ± 0.11) × 10?15 cm3 molecule?1 s?1 (CHF2Cl reference) and (2.12 ± 0.11) × 10?15 cm3 molecule?1 s?1 (CH2FCF3 reference). These data are in agreement with each other within the estimated experimental uncertainties. The Arrhenius rate constant determined from the kinetic data was K1 = (4.71 ± 0.94) × 10?13 exp[?(1630 ± 80)/T] cm3 molecule?1 s?1. Using kinetic data for the reaction of tropospheric CH3CCl3 with OH radicals [k1 (272 K) = 6.0 × 10?15 cm3 molecule?1 s?1, tropospheric lifetime of CH3CCl3 = 6.0 years], we estimated the tropospheric lifetime of CF3CF2CF2CF2CF2CHF2 through reaction with OH radicals to be 31 years. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 26–33, 2004 相似文献
2.
Linear and nonlinear optical properties of racemic (±)2-(α-methylbenzylamino)-5-nitropyridine ((±)MBANP) single crystals have been comprehensively investigated and compared with those of the enantiomorph (–)2-(α-methylbenzylamino)-5-nitropyridine ((–)MBANP) crystals. (±)MBANP crystal exhibits very high chemical and physical stability, but relatively small nonlinear optical coefficients (d31 = 6.8 pm/V, d32 = 4.7 pm/V, d33 = 0.84 pm/V). A comparison between the nonlinear optical coefficients of (±)MBANP and (–)MBANP demonstrates the validity of the oriented-gas model in molecular crystals that neglects all the contributions from intermolecular interaction. 相似文献
3.
Kenichi Oyaizu Junya Katoh Fumiaki Suzuki Mitsutoshi Jikei Kimihisa Yamamoto Hiroyuki Nishide Eishun Tsuchida 《先进技术聚合物》1991,2(3):155-159
Oligo(phenylene sulfide) (OPS) containing one disulfide bond at the end of the chain, which was obtained by the oxidative polymerization of diphenyl disulfide, had a relatively low Td10%(temperature for 10% weight loss) of 412 °C because of degradation of the disulfide bond. But this thermal cleavage of the disulfide bond promoted the curing reaction through thiophenoxy radical formation. OPS was allowed to react with diiodobenzene at 220 °C. The thermal stability of OPS was improved through the consumption of the disulfide bond and the coupling of the chain. 相似文献
4.
5.
6.
In order to interpret abrupt changes of distributions of orientations andmagnitudes of hyperfine fields in Mössbauer measurements of57Fe in YFeMnO4, a model is proposed. The origin is assumed to be not static but dynamic. Fluctuating fields are caused by spins in a fully frustrated spin system, namely, a Heisenberg spin system on a triangular lattice in a two-dimensional antiferromagnet. Extending the stochastic theory for the fluctuation between two states to that among many states with a Gaussian distribution, we fit the spectra with three parameters, hyperfine fieldH
hf, correlation time c, andwidth of fluctuating field , within a limited condition of =c=1. Obtained results represent the characteristic features of Mössbauer spectra well, in spite of a simplified model. 相似文献
7.
Takeshi Wada Hiroshi Sekiya Sueo Machi 《Journal of polymer science. Part A, Polymer chemistry》1975,13(10):2375-2389
The effects of temperature, dose rate, and monomer concentration on the heterogeneous polymerization of acrylamide in acetone–water mixtures have been studied. Heterogeneous polymerization takes place in mixtures containing less than 60 vol-% water. The polymerization is steady in acetone and nonsteady in acetone an nonsteady in mixtures containing 10–50 vol-% water. The average rate of polymerization is highest in mixtures with about 20 vol-% water. Polymer molecular weight increases with the increasing water content in range 0–10 vol-% and does not change in the range of 30–70 vol-% water. For the polymerization in acetone and an acetone–water 60/40 mixture the activation energies are 2.3 and ?1.8 kcal/mole, the dose rate exponents of rate are 0.78 and 0.52, and the monomer concentration exponents of rate are 0.5 and 1.6, respectively. The polymer molecular weight increases with decreasing dose rate, decreasing temperature, and increasing monomer concentration. These results are discussed in connection with the mechanism of heterogeneous polymerization and the solvent effect. 相似文献
8.
Heng-Dao Quan Hui-E Yang Masanori Tamura Akira Sekiya 《Journal of fluorine chemistry》2007,128(3):190-195
In this report, a simple process for preparing HFC-245fa through the reaction of 1,1,1,3,3-pentachloropropane (PCP) and anhydrous HF via two-step vapor-phase catalytic fluorination is described. The antimony pentafluoride catalyst was supported on inert porous materials to improve the catalytic activity. The resulting process catalyst not only exhibited high catalytic activity and excellent thermo-stability, but also improved the performance of SbF5, in terms of hygroscopicity and corrosion. 相似文献
9.
The electronic structure of the lower states of a trigonal Cr3+ pair and Mo3+ pair, which occur in the Cs3M2Cl9 crystal (M=Cr,Mo), were studied by theoretical calculations carried out according to several methods: multireference singly and doubly excited configuration interaction, second-order configuration interaction, and multireference coupled-pair approximation. We employed a model of a [M2Cl9]3- anion embedded in a cage of point charges, which were arranged so as to simulate the anion in the crystal. The model core potential was utilized, where the relativistic effect was included for Mo. Results of the Cr complex showed that there were no direct bonds between the Cr metals. The lower electronic spectra of the [Cr2Cl9]3- ion were interpreted in terms of the electronic spectra of [CrCl6]3-. The lowest state of simultaneous excitation in both metals was considered. The [Mo2Cl9]3- ion exhibited a single direct bond between the metals. Reflecting this single bond, the observed singlet-triplet splitting was much larger than that in the case of Cr and the calculated splitting was in good agreement with the observed one. We account for the electronic spectra of the [Mo2Cl9]3- complex, which exhibited quite different features in the electronic excitation spectra in comparison with those of the Cr complex. 相似文献
10.
Kouichi Ohe Tomomi Yokoi Koji Miki Fumiaki Nishino Sakae Uemura 《Journal of the American Chemical Society》2002,124(4):526-527
The reaction of cis vicinal acetylethynylcyclopropanes 1 with a catalytic amount of M(CO)5(THF) (M = Cr or W) in the presence of Et3N at room temperature gave ortho-substituted phenols 7 in good yields as valence isomerized products. In the absence of Et3N the reactions did not work at all. The reaction of a cyclopropane having an ester or an amide instead of an acetyl moiety with M(CO)5(THF) did not take place, whereas an ethynylvinylcyclopropane gave a mixture of 1- and 2-substituted 1,3,5-cycloheptatrienes. These valence isomerization reactions are assumed to proceed via the formation of vinylidene-metal intermediates 2 from terminal alkynyl moieties followed by [3,3]sigmatropy of 2 to give seven-membered carbene complexes 3. 相似文献