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91.
Alan C. Hopkinson Min H. Lien Imre G. Csizmadia Keith Yates 《Theoretical chemistry accounts》1980,55(1):1-14
The geometries of the 2-aminoethyl cation and the isomeric protonated aziridine have been optimized using ab initio molecular orbital calculations employing the split-valence shell 4-31G basis set. The protonated aziridine is computed to be the more stable ion by 46.5 kcal/mole (4-31G level) and 44.9 kcal/mole (double-zeta basis set). The profile to interconversion is found to have a barrier of less than 15 kcal/mole (relative to the 2-aminoethyl cation) and this profile is compared with those computed for the similar ions XCH2CH
2
+
where X=OH, F, SH and Cl. 相似文献
92.
Kathleen V Kilway Keith A Lindgren James A Watson Jr. Robert D Ingalls Robert A Pascal Jr. 《Tetrahedron》2004,60(10):2433-2438
Oxygenation of 2,5,9,12-tetra(tert-butyl)diacenaphtho[1,2-b:1′,2′-d]-thiophene (1, C40H44S) by peracids gave the cyclic sulfonic ester 4 (2,7,10,13-tetra(tert-butyl)diacenaphtho[1,2-c:1′,2′-e]oxathiin 5,5-dioxide, C40H44O3S) which, when heated in nitrobenzene, is converted into a complex, macrocyclic anhydride 3 (C80H88O3), which is derived from two molecules of 4. Further investigation found a likely intermediate in this reaction, 4,4′,7,7′-tetra(tert-butyl)-1,1′-biacenaphthylenylidene-2,2′-dione (5, C40H44O2), apparently formed from 4 by additional oxidation. Anhydride 3 plausibly arises by Diels-Alder reaction of 4 and 5 followed by several ring fragmentations. The structures of 3, 4, and 5 were unambiguously established by X-ray crystallography. 相似文献
93.
Quantum yield of the iodide-iodate chemical actinometer: dependence on wavelength and concentrations
Rahn RO Stefan MI Bolton JR Goren E Shaw PS Lykke KR 《Photochemistry and photobiology》2003,78(2):146-152
The quantum yield (QY) of the iodide-iodate chemical actinometer (0.6 M KI-0.1 M KIO3) was determined for irradiation between 214 and 330 nm. The photoproduct, triiodide, was determined from the increase in absorbance at 352 nm, which together with a concomitant measurement of the UV fluence enabled the QY to be calculated. The QY at 254 nm was determined to be 0.73 +/- 0.02 when calibration was carried out against a National Institute of Standards and Technology traceable radiometer or photometric device. At wavelengths below 254 nm the QY increased slightly, leveling off at -0.80 +/- 0.05, whereas above 254 nm the QY decreases linearly with wavelength, reaching a value of 0.30 at 284 nm. In addition, the QY was measured at different iodide concentrations. There is a slight decrease in QY going from 0.6 to 0.15 M KI, whereas below 0.15 M KI the QY drops off sharply, decreasing to 0.23 by 0.006 M KI. Calibration of the QY was also done using potassium ferrioxalate actinometry to measure the irradiance. These results showed a 20% reduction in QY between 240 and 280 nm as compared with radiometry. This discrepancy suggests that the QY of the ferrioxalate actinometer in this region of the spectrum needs reexamination. 相似文献
94.
Keith R. Roby 《International journal of quantum chemistry》1972,6(1):101-123
An exact cluster expansion of many electron wave functions is derived, beginning with a finite linear combination of Slater determinants rather than the more usual single determinant. This general cluster expansion is found to apply both in the case where all possible Slater determinants from a finite set of spin orbitals are included in the linear combination, and in the case where the number of determinants is restricted. The special properties of that finite linear combination of determinants closest to the exact wave function in the least squares sense are studied. These properties lead to the derivation of a general correlated wave functions method, illustrating again the close relationship between methods of this type and cluster expansion theory. Additional approximations, necessary for practical calculations, are set out. 相似文献
95.
Zhang L Cradlebaugh J Litwinienko G Smart BE Ingold KU Dolbier Jr WR 《Organic & biomolecular chemistry》2004,2(5):689-694
A combination of laser flash photolysis and competitive kinetic methods have been used to measure the absolute bimolecular rate constants for hydrogen atom abstraction in water from a variety of organic substrates including alcohols, ethers, and carboxylic acids by the perfluoroalkyl radical, *CF(2)CF(2)OCF(2)CF(2)SO(3)(-) Na(+). Comparison, where possible, of these rate constants with those previously measured for analogous reactions in the non-polar organic solvent, 1,3-bis(trifluoromethyl)benzene (J. Am. Chem. Soc, 1999, 121, 7335) show that the alcohols react 2-5 times more rapidly in the water solvent and that the ethers react at the same rate in both solvents. A transition state for hydrogen abstraction that is more reminiscent of an "intimate ion pair" than a "solvent separated ion pair" is invoked to explain these modest solvent effects. 相似文献
96.
The comparative reaction chemistry between first and second derivative paraelement analogs ( (CF3)2PH, (CF3S)2PH, CF3SH, CF3SSH, CF3SNH2, (CF3S)2NH, (CF3S) 3N) and F-N-isopropylacetimidoyl chloride [CF3CCl=NCF(CF3)2, I] has been investigated. Reaction schemes are presented. The reactions of I with NH3 and NaI are also reported. Analytical data is provided for previously unreported compounds along with more detailed analysis of known compounds. 相似文献
97.
Alan C. Hopkinson Min H. Lien Keith Yates Imre G. Csizmadia 《Theoretical chemistry accounts》1977,44(4):385-398
The geometries of the 2-chloroethyl and ethylenechloronium cations, two possible intermediates in the electrophilic addition of chlorine to ethylene, have been fully optimized using ab initio molecular orbital calculations employing the split valence shell 4-31G basis set.These geometries were then used to compute more accurate wave functions using Dunning's double-zeta basis set. The bridged chloronium ion was found to be more stable by 9.35 kcal/mole, the opposite order of stability from the C2H4F+ ions. Interconversion of the two C2H4Cl+ cations was computed to have a barrier of 6.25 kcal/mole.The activation energy for this chlorination reaction, using the ethylenechloronium cation and a chlorine anion at infinite separation as the model for the activated complex, was computed to be 128.7 kcal/mole, showing that this is not a feasible gas phase reaction. 相似文献
98.
Prem Paul Singh Jan Spitzer Robert M. McKay Keith G. McCurdy Loren G. Hepler 《Thermochimica Acta》1978,24(1):111-115
We have made calorimetric and density measurements leading to apparent molar heat capacities and volumes of dilute aqueous solutions of silver nitrate and silver perchlorate at 298 K. Resulting apparent molar properties at infinite dilution are the following: φoc(AgNO3) = ? 36.8 J K?1 mol?1, φov(AgNO3) = 29.1 cm3 mol?1, φoc(AgClO4) = 11.0 J K?1 mol?1, and φov(AgClO4) = 43.5 cm3 mol?1. 相似文献
99.
A total of 29 transition metals (all except Tc), all as ions M(+), have been reacted with gaseous S(8). The reactivities and reaction products provide a unique set of comparative data on a fundamental reaction of the elements. The results underlie the interpretation of many other processes and compounds in condensed phases. Series of product ions [MS(y)()](+) are formed, with y generally starting at 4, and increasing with time through 8 up to 10, 12, 16, or 21 (for La(+)). A general mechanism is proposed, in which the first {MS(8)}(+) encounter complex is reactive and undergoes S-S bond scission and rearrangement around the metal, such that [MS(8)](+) is not an early product. The early transition metals react faster than later members of the series, and third row metals react about twice as fast as first row metals. The metals which are more chalcophilic in condensed-phase chemistry are apparently less so as M(+); Hg(+) does not form observable [HgS(y)()](+) (except for a very low yield of [HgS(3)](+)) and is remarkably less reactive with sulfur than most of the other metal ions. Simple electron transfer between M(+) and S(8) does not occur except possibly for Ir(+), but S(8)(+) is sometimes observed and is believed to be formed by electron transfer from S(8) to some [MS(y)()](+) complexes. Interpretation of the rates of reaction of the ions of groups 3, 4, and 5 with S(8) is complicated because they react with adventitious water in the cell forming oxo-species. The results are discussed in the context of condensed-phase metal polysulfide chemistry. 相似文献
100.
Stereoselective syntheses of novel 5,6-difunctionalized-2-azabicyclo[2.1.1]hexanes containing 5-anti-fluoro or hydroxyl in one methano bridge and a variety of syn- or anti-chloro, fluoro, hydroxy, methyl, or phenyl substituents in the other methano bridge have been effected. Rearrangements of iodides to alcohols were initiated using Selectfluor. Rearrangement of alcohols to fluorides was initiated using Deoxo-Fluor. Ring opening of 2-azabicyclo[2.2.0]hex-5-ene exo-epoxide with organocopper reagents is regioselective at C(5). 相似文献