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Fera A Dolbnya IP Grubel G Muller HG Ostrovskii BI Shalaginov AN de Jeu WH 《Physical review letters》2000,85(11):2316-2319
Coherent dynamic x-ray scattering has been used to study the thermally excited layer fluctuations in freely suspended smectic films of the compound 4O.8. Using 8-keV x rays and films with a thickness around 0.3 &mgr;m we resolve relaxation times down to a few &mgr;s. A combination of damped and oscillatory behavior is observed for the layer undulations, which can be attributed to inertial effects. These are due to the surface contribution to the free energy which cannot be disregarded for thin films. 相似文献
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van Eis MJ van Der Linde BS de Kanter FJ de Wolf WH Bickelhaupt F 《The Journal of organic chemistry》2000,65(14):4348-4354
In contrast to the terminal phosphinidene complex PhPW(CO)(5) (2), which adds to [5]metacyclophane (1) in a 1,4-fashion, dichlorocarbene preferentially adds in a 1,2-fashion to the formal "anti-Bredt" type double bond of the aromatic ring of 1 to afford the norcaradiene 11b, which immediately rearranges to the bridged cycloheptatriene 12b and further by a [1,5] sigmatropic chlorine migration to the isomeric 13b as the first observable product. More slowly, the latter isomerizes via a dissociative mechanism to give 15b. A computational study supports the notion that the [1,5] chlorine migration in the rearrangement 12b --> 13b, for which an activation barrier of 70.2 kJ mol(-)(1) was calculated, is essentially concerted with minor charge separation. In contrast, the analogous [1,5] chlorine migration in the flat model compound 7,7-dichlorocycloheptatriene (12a) displays features of a dissociative pathway. 相似文献
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The influence of various types of background electrolytes (NaCl, NaNO(3), and NaClO(4)) on the proton adsorption and on the adsorption of sulfate and phosphate on goethite have been studied. Below the PZC the proton adsorption on goethite decreases in the order Cl>NO(3)>ClO(4). The decreasing proton adsorption affects the adsorption of oxyanions on goethite. Anion adsorption of strongly binding polyvalent anions is lower in the studied electrolytes in the order Cl相似文献
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Metal (hydr)oxides have different types of surface groups. Fluoride ions have been used as a probe to assess the number of surface sites. We have studied the F(-) adsorption on goethite by measuring the F(-) and H(+) interaction and F(-) adsorption isotherms. Fluoride ions exchange against singly coordinated surface hydroxyls at low F(-) concentrations. At higher concentrations also the doubly coordinated OH groups are involved. The replacement of a surface OH(-) by F(-) suggests that all F charge (-1) is located at the surface in contrast to oxyanions which have a charge distribution in the interface due to the binding structure in which the anion only partially coordinates with the surface. Analysis of our F(-) data with the CD-MUSIC approach shows that the formation of the fluoride surface complex is accompanied by a redistribution of charge. This is supposed to be due to a net switch in the H bonding as a result of the change of the type of surface complex from donating (FeOH, FeOH(2)) to proton accepting (FeF). The modeled redistribution of charge is approximately equivalent with the change of a donating H bond into an accepting H bond. At high F(-) concentrations precipitation of F(-), as for instance FeF(3)(s), may occur. The rate of formation is catalyzed by the presence of high electrolyte concentrations. Copyright 2000 Academic Press. 相似文献
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ARC-length method for differential equations 总被引:1,自引:0,他引:1
IntroductionTheordinaryandpartialdiferentialequationsofcontinuumproblemareoftenwithcertaintypesofsingularityasstifproperty,or... 相似文献