Complex dynamic behavior of fluctuating smectic- A films as studied by scattering with coherent X-rays

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.     

Dichlorocarbene Addition to

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.     

Electrolyte Anion Affinity and Its Effect on Oxyanion Adsorption on Goethite

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