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221.
Edgar Niecke Andr Fuchs Martin Nieger 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》1999,111(20):3213-3216
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Gokulakrishnan Soundararajan Cyril Koughia Andy Edgar Chris Varoy Safa Kasap 《Journal of Non》2011,357(11-13):2475-2479
We report the optical properties of a fluorochlorozirconate (FCZ) glass with the composition 53% ZrF4, 20% NaF, 3.5% AlF3, 3% LaF3, 0.5% InF3, (20 ? x)% BaCl2, x% BaF2 with x varying from 0% to 2%, and doped with various amounts of trivalent erbium by the addition of ErCl3. Annealing of the as-prepared glass in inert (N2) or reducing (5%H2 + 95%Ar) atmospheres at temperatures that ensure the conversion of the glass into a glass-ceramic by the nucleation of BaCl2 nanocrystals, does not significantly change any of Er3+ related absorption and photoluminescence (PL) characteristics. We have carried out a Judd–Ofelt analysis of the absorption spectra and obtained Ω2 = (1.92 ± 0.3) × 10? 20 cm2, Ω4 = (0.88 ± 0.16) × 10? 20 cm2 and Ω6 = (0.59 ± 0.08) × 10? 20 cm2, and also the radiative lifetimes of the 4I13/2→4I15/2, 4I11/2→4I15/2 and 4S3/2→4I15/2 bands. The radiative lifetime from the Judd–Ofelt analysis for the 4I13/2→4I15/2 band is in good agreement with the experimentally measured PL decay time. The examination of the optical properties of powdered samples with different average particle size does not show any photon trapping effects. We have determined the spectral absorption and emission cross-sections and then estimated the possible spectral optical gain for varying degrees of relative populations of the 4I13/2 and 4I15/2 manifolds. 相似文献
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Wolfgang Marterer Horst Prinzbach Grety Rihs Jakob Wirz Jaques Lecoultre Edgar Heilbronner 《Helvetica chimica acta》1988,71(8):1937-1965
The propensity of the N?N bond to undergo photo [2 + 2] cycloadditions has been further explored. In the specifically designed 1,5-azo/enes 1–3 , no [2 + 2] cycloaddition has been observed upon either direct or sensitized excitation with light of various wave lengths at temperatures down to 77 K, in line with expectations based on X-ray ( 1 : d = 2.71 Å, ω = 129°) and PE measurements ( 1 : I1 = 8.00, I2 = 9.05 eV; 2 ; I1 = 8.00, I2 = 9.25eV). The steric/stereoelectronic demands for the participation of the N?N bond in pericyclic reactions are clearly more stringent than those for the C?C bond. 相似文献
227.
Armando Herize José R. Mora Jesus Lezama Edgar Marquez Tania Córdova Gabriel Chuchani 《Journal of Physical Organic Chemistry》2009,22(2):170-176
The elimination kinetic of methyl carbazate in the gas phase was determined in a static system over the temperature range of 340–390 °C and pressure range of 47–118 Torr. The reaction is homogeneous, unimolecular, and obeys a first order rate law. The decomposition products are methyl amine, nitrous acid, and CO gas. The variation of the rate coefficients with temperatures is given by the Arrhenius expression: log k1 (s?1) = (11.56 ± 0.34) ? (180.7 ± 4.1) kJ mol?1(2.303 RT)?1. The estimated kinetics and thermodynamics parameters are in good agreement to the experimental values using B3LYP/6‐31G (d,p), and MP2/6‐31G (d,p) levels of theory. These calculations imply a molecular mechanism involving a concerted non‐synchronous quasi three‐membered ring cyclic transition state to give an unstable intermediate, 1,2‐oxaziridin‐3‐one. Bond order analysis and natural charges implies that polarization of O (alkyl)? C (alkyl) bond of the ester is rate determining in this reaction. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
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Edgar Marquez Alexis Maldonado Felix Rosas Beatriz Ramirez Gabriel Chuchani 《Molecular physics》2014,112(3-4):462-473
The kinetics and mechanisms of thermal decomposition of phenyl acetate and p-tolyl acetate in the gas phase were studied by means of electronic structure calculations using density functional theory methods: B3LYP/6-31G(d,p), B3LYP/6-31++G(d,p), B3PW91/6-31G(d,p), B3PW91/6-31++G(d,p), MPW1PW91/6-31G(d,p), MPW1PW91/6-31++G(d,p), PBE/6-31G(d,p) and PBE/6-31++G(d,p). Two possible mechanisms have been considered: mechanism A is a stepwise process involving electrocyclic [1,5] hydrogen shift to eliminate ketene through concerted six-membered cyclic transition-state structure, followed by tautomerisation of cyclohexadienone or by 4-methyl cyclohexadienone intermediate to give the corresponding phenol. Mechanism B is a one-step concerted [1,3] hydrogen shift through a four-membered cyclic transition-state geometry, to produce ketene and phenol or p-cresol. Theoretical calculations showed reasonable agreement with experimental activation parameters when using the Perdew, Burke and Ernserhof (PBE)functional, through the stepwise [1,5] hydrogen-shift mechanism. For mechanism B, large deviation for the entropy of activation was observed. No experimental data were available for p-tolyl acetate; however, theoretical calculations showed similar results to phenyl acetate, thus supporting the stepwise mechanism for both phenyl acetate and p-tolyl acetate. 相似文献
230.
Plutonium-enriched layer has been observed in corroded spent uranium oxide fuel (CSNF). These Pu-enriched regions were examined with analytical transmission electron microscopy combined with electron energy-loss spectroscopy (EELS). The enriched region also contained U, Am, Ru, Zr, but only minor enrichment of rare earth elements. The Pu, possibly as Pu(V) according to EELS measurements, was dispersed within re-precipitated uranium oxide (identified as U3O8) nano-crystals between U(VI) secondary phases and the CSNF surface. The U, Pu, and Am enrichment was observed in the corrosion products with tests on different nuclear fuels. This may have implications for the long-term behavior of CSNF under storage in a geologic waste repository. Furthermore, there may be an increased potential for the generation of Pu-bearing colloids from this type of weathered CSNF. 相似文献