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排序方式: 共有137条查询结果,搜索用时 15 毫秒
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An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol?1)·T?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH3 group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition. 相似文献
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Abstract Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood. 相似文献
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A deductive approach to the solution of the problem of optimal pairs trading from the viewpoint of stochastic control with time‐dependent parameters 下载免费PDF全文
K. Charalambous C. Sophocleous J. G. O'Hara P. G. L. Leach 《Mathematical Methods in the Applied Sciences》2015,38(17):4448-4460
In a fairly recent paper (2008 American Control Conference, June 11‐13, 1035‐1039), the problem of dealing with trading in optimal pairs was treated from the viewpoint of stochastic control. The analysis of the subsequent nonlinear evolution partial differential equation was based upon a succession of Ansätze, which can lead to a solution of the terminal‐value problem. Through an application of the Lie Theory of Continuous Groups to this equation, we show that the Ansätze are based upon the underlying symmetries of the equation (their (14)). We solve the problem in a more general context by allowing the parameters to be explicitly time dependent. The extension means thatmore realistic problems are amenable to the samemode of solution. Copyright © 2014 JohnWiley & Sons, Ltd. 相似文献
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Andrikopoulos PC Armstrong DR Clegg W Gilfillan CJ Hevia E Kennedy AR Mulvey RE O'Hara CT Parkinson JA Tooke DM 《Journal of the American Chemical Society》2004,126(37):11612-11620
Subjecting ferrocene, ruthenocene, or osmocene to the synergic amide base sodium-magnesium tris(diisopropylamido) affords a unique homologous series of metallocene derivatives of general formula [(M(C(5)H(3))(2))Na(4)Mg(4)(i-Pr(2)N)(8)] (where M = Fe (1), Ru (2), or Os (3)). X-ray crystallographic studies of 1-3 reveal a common molecular "inverse crown" structure comprising a 16-membered [(NaNMgN)(4)](4+) "host" ring and a metallocenetetraide [M(C(5)H(3))(2)](4-) "guest" core, the cleaved protons of which are lost selectively from the 1, 1', 3, and 3'-positions. Variable-temperature NMR spectroscopic studies indicate that 1, 2, and 3 each exist as two distinct interconverting conformers in arene solution, the rates of exchange of which have been calculated using coalescence and EXSY NMR measurements. 相似文献
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Hevia E Gallagher DJ Kennedy AR Mulvey RE O'Hara CT Talmard C 《Chemical communications (Cambridge, England)》2004,(21):2422-2423
Only two-fold amination occurs when 3 molar equivalents of TMPH are offered to a 1:1 BuNa-Bu2Mg mixture; adding TMEDA gives the mixed alkyl amide [(TMEDA)Na(mu-Bu)(mu-TMP)Mg(TMP)], which itself affords the phenyl-bridged analogue when reacted with benzene. 相似文献
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We demonstrate quasi-optical, diffraction-limited two-dimensional image production by means of reflected pulses of terahertz (THz) radiation. A spherical mirror is used to form a real one-to-one THz image of two 1-mm-diameter steel spheres, which is then scanned over a THz receiver. Diffraction-limited spatial (cross-range) resolution and THz pulse range resolution are simultaneously observed. 相似文献
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We use an all-optical trap to confine a strongly attractive two-state mixture of lithium fermions. By measuring the rate of evaporation from the trap, we determine the effective elastic scattering cross section 4pia(2) to show that the magnitude of the scattering length |a| is very large, in agreement with predictions. We show that the mixture is stable against inelastic decay provided that a small bias magnetic field is applied. For this system, the s-wave interaction is widely tunable at low magnetic field, and can be turned on and off rapidly via a Raman pi pulse. Hence, this mixture is well suited for fundamental studies of an interacting Fermi gas. 相似文献