全文获取类型
收费全文 | 191篇 |
免费 | 5篇 |
专业分类
化学 | 107篇 |
晶体学 | 1篇 |
力学 | 3篇 |
数学 | 50篇 |
物理学 | 35篇 |
出版年
2020年 | 3篇 |
2019年 | 3篇 |
2018年 | 2篇 |
2016年 | 6篇 |
2015年 | 8篇 |
2014年 | 7篇 |
2013年 | 8篇 |
2012年 | 7篇 |
2011年 | 16篇 |
2010年 | 2篇 |
2009年 | 2篇 |
2008年 | 17篇 |
2007年 | 6篇 |
2006年 | 4篇 |
2005年 | 4篇 |
2004年 | 3篇 |
2003年 | 7篇 |
2002年 | 6篇 |
2001年 | 4篇 |
2000年 | 4篇 |
1999年 | 2篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 3篇 |
1995年 | 3篇 |
1993年 | 4篇 |
1992年 | 2篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 6篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1977年 | 3篇 |
1975年 | 4篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1971年 | 1篇 |
1970年 | 1篇 |
1969年 | 1篇 |
1968年 | 1篇 |
1964年 | 1篇 |
1963年 | 1篇 |
1961年 | 1篇 |
1958年 | 1篇 |
1954年 | 1篇 |
排序方式: 共有196条查询结果,搜索用时 11 毫秒
41.
42.
Hanno Hertz 《Zeitschrift für Physik A Hadrons and Nuclei》1975,274(4):289-291
Optical excitation functions were measured for Xenon emission lines. The Xe III 5s 5p 5 levels are excited in two different processes, by a direct two electron ejection and by a 4d ionization followed by an Auger decay. An emission line found at 1089.0 Å is excited by 4d ionization. This line is assigned to the Xe III transition 5s5p 5 1 P 0 —5s 0 5p 6 1 S. The1 S energy level amounts to 26.14 eV. 相似文献
43.
Michael M. Konnick Brian G. Hashiguchi Deepa Devarajan Nicholas C. Boaz T. Brent Gunnoe John T. Groves Niles Gunsalus Daniel H. Ess Roy A. Periana 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(39):10658-10662
Direct partial oxidation of methane, ethane, and propane to their respective trifluoroacetate esters is achieved by a homogeneous hypervalent iodine(III) complex in non‐superacidic (trifluoroacetic acid) solvent. The reaction is highly selective for ester formation (>99 %). In the case of ethane, greater than 0.5 M EtTFA can be achieved. Preliminary kinetic analysis and density functional calculations support a nonradical electrophilic CH activation and iodine alkyl functionalization mechanism. 相似文献
44.
Accurate barriers for the 1,3-dipolar cycloadditions of ozone with acetylene and ethylene have been determined via the systematic extrapolation of ab initio energies within the focal point approach of Allen and co-workers. Electron correlation has been accounted for primarily via coupled cluster theory, including single, double, and triple excitations, as well as a perturbative treatment of connected quadruple excitations [CCSD, CCSD(T), CCSDT, and CCSDT(Q)]. For the concerted [4 + 2] cycloadditions, the final recommended barriers are DeltaH(0K) = 9.4 +/- 0.2 and 5.3 +/- 0.2 kcal mol(-1) for ozone adding to acetylene and ethylene, respectively. These agree with recent results of Cremer et al. and Anglada et al., respectively. The reaction energy for O3 + C2H2 exhibits a protracted convergence with respect to inclusion of electron correlation, with the CCSDT/cc-pVDZ and CCSDT(Q)/cc-pVDZ values differing by 2.3 kcal mol-1. Recommended enthalpies of formation (298 K) for cycloadducts 1,2,3-trioxole and 1,2,3-trioxolane are +32.8 and -1.6 kcal mol(-1), respectively. Popular composite ab initio approaches [CBS-QB3, CBS-APNO, G3, G3B3, G3(MP2)B3, G4, G4(MP3), and G4(MP2)] predict a range of barrier heights for these systems. The CBS-QB3 computed barrier for ozone and acetylene, DeltaH(0K) = 4.4 kcal mol(-1), deviates by 5 kcal mol(-1) from the focal point value. CBS-QB3 similarly underestimates the barrier for the reaction of ozone and ethylene, yielding a prediction of only 0.7 kcal mol(-1). The errors in the CBS-QB3 results are significantly larger than mean errors observed in application to the G2 test set. The problem is traced to the nontransferability of MP2 basis set effects in the case of these reaction barriers. The recently published G4 and G4(MP2) approaches perform substantially better for O3 + C2H2, predicting enthalpy barriers of 9.0 and 8.4 kcal mol(-1), respectively. For the prediction of these reaction barriers, the additive corrections applied in the majority of the composite approaches considered lead to worse agreement with the reference focal point values than would be obtained relying only on single point energies evaluated at the highest level of theory utilized within each composite method. 相似文献
45.
46.
47.
48.
In part II of this tutorial, the investigated approaches of estimating the limit of detection (LOD) are applied to experimental data from LC-MS measurements. Important practical aspects specific to LC-MS and related to LOD are reviewed. The results of different tests of estimating linearity and scedasticity are compared. LOD estimates obtained with different approaches (for both simple characterization of the analysis method and accurate interpretation of the results) are applied to the data and the obtained values are compared. As a conclusion, a decision tree is proposed for estimating LOD for analytical methods using the LC-MS technique. 相似文献
49.
Heilbronn conjectured that given arbitrary
n points in the 2-dimensional
unit square [0, 1]2, there must be
three points which form a triangle of area at most
O(1/n2). This
conjecture was disproved by a nonconstructive argument of
Komlós, Pintz and Szemerédi [10] who showed that for every
n there is a configuration of
n points in the unit square
[0, 1]2 where all triangles have area
at least (log
n/n2).
Considering a generalization of this problem to dimensions
d3, Barequet [3] showed for
every n the existence of
n points in the
d-dimensional unit cube [0,
1]d such that the minimum
volume of every simplex spanned by any (d+1) of these n points is at least
(1/nd). We improve on this
lower bound by a logarithmic factor (log n). 相似文献
50.
Activation barriers and reaction energetics for the three main classes of 1,3-dipolar cycloadditions, including nine different reactions, were evaluated with the MPW1K and B3LYP density functional methods, MP2, and the multicomponent CBS-QB3 method. The CBS-QB3 values were used as standards for 1,3-dipolar cycloaddition activation barriers and reaction energetics, and the density functional theory (DFT) and MP2 methods were benchmarked against these values. The MPW1K/6-31G* method and basis set performs best for activation barriers, with a mean absolute deviation (MAD) value of 1.1 kcal/mol. The B3LYP/6-31G* method and basis set performs best for reaction enthalpies, with a MAD value of 2.4 kcal/mol, while the MPW1K method shows large errors for reaction energetics. The MP2 method gives the expected systematic underestimation of barriers. Concerted and nearly synchronous transition structures are predicted by all DFT and MP2 methods. Also reported are revised estimated 0 K experimental activation enthalpies for a standard set of hydrocarbon pericyclic reactions and updated comparisons to experiment for DFT, ab initio, and multicomponent methods. B3LYP and MPW1K methods with MAD values of 1.5 and 2.1 kcal/mol, respectively, fortuitously outperform the multicomponent CBS-QB3 method, which has a MAD value of 2.3. The MAD value of the O3LYP functional improves to 2.4 kcal/mol from the previously reported 3.0 kcal/mol. 相似文献