Initial oxidation kinetics of copper (1 1 0) film investigated by in situ UHV-TEM

Previous studies of the initial stage of oxidation on clean single crystal of Cu(1 0 0) have been extended to the case of the Cu(1 1 0) surface. The dynamic observation of the nucleation and growth of Cu oxide by means of in situ ultra high vacuum transmission electron microscopy (UHV-TEM) shows a highly enhanced oxidation rate on Cu(1 1 0) surface as compared to Cu(1 0 0). The kinetic data on the nucleation and growth of the three-dimensional oxide islands agree well with our heteroepitaxial model of surface diffusion of oxygen.     

Thermal and dilute-solution properties of zwitterionic copolymers

We report the synthesis, characterization, thermal and dilute-solution properties of zwitterionic copolymers of the sulfobetaine type, where the proportion of ionic groups is varied over a wide range. Two different structures are considered: poly (2-vinyl pyridine sulfopropyl betaine) and poly (4-vinyl pyridine sulfopropyl betaine). Synthesis is carried out to obtain random copolymers which are further characterized and their ionic content determined. At low proportions of ionic groups, the behavior is similar to that observed in ionomers, with substantial differences between the two structures, Increased interaction among the zwitterionic groups at higher charge densities is evidenced, which leads to the formation of clusters and agglomerates. An increase in the intrinsic viscosity with salt content in aqueous solutions is also observed. This behavior is analogous to that of homopolymers with 100% ionic content, but with particular features of interest.     

The influence of the liquid crystalline core geometry on the mesogenicity of novel chiral 2-(4-substituted-phenoxy)propanonitriles

The synthesis and characterization of seven novel (R)-2-(4-substituted-phenoxy)propanonitriles are described. The propanonitriles were prepared to evaluate their potential use as thermochromics and ferroelectric dopants, as well as to determine their twist sense properties. The materials exhibit smectic and chiral nematic phases of high thermal stability; the mesogenic behaviour of the nitriles is directly related to the type of two-ring core unit employed. The effects of the different molecular geometries and polarizabilities of the liquid crystalline cores on mesophase stability are discussed, particularly in relation to other members of this series. The chiral nematic phase of the propanonitriles is assigned as having a left-handed twist sense from contact preparation studies, and this is in agreement with rules relating absolute configuration and molecular structure to helical twist sense.     

Computational advances in organic chemistry: Molecular structure and reactivity. Edited by C. Ögretir and I. G. Csizmadia,NATO ASI Series C,Vol, 330.

We here report an AM 1 study for the reaction of different types of radicals with the acetone enolate ion 1 and other ambident nucleophiles. The theoretical reactivity order determined is phenyl > methyl > tert-butyl ? bicyclo-[2.2.1]hept-1-yl. The activation energy for the coupling of aliphatic radicals is ascribed mainly to nonbonded interactions. Considering possible solvent effects, we propose the same order of reactivity in solution. The coupling reaction of phenyl radical with 1 is an exothermic process with nonactivation energy in the gas phase. Any energy barrier in solution is here ascribed to desolvation of the anion. The regiochemistry of the coupling of radicals with ambident nucleophiles such as 1 , phenoxide, or phenylamide anions is also explained on a theoretical basis. © 1992 John Wiley & Sons, Inc.     

Flat rank of automorphism groups of buildings

The flat rank of a totally disconnected locally compact group G, denoted flat-rk(G), is an invariant of the topological group structure of G. It is defined thanks to a natural distance on the space of compact open subgroups of G. For a topological Kac-Moody group G with Weyl group W, we derive the inequalities alg-rk(W) ≤ flat-rk(G) ≤ rk(|W|₀). Here, alg-rk(W) is the maximal Z-rank of abelian subgroups of W, and rk(|W|₀) is the maximal dimension of isometrically embedded flats in the CAT0-realization |W|₀. We can prove these inequalities under weaker assumptions. We also show that for any integer n ≥ 1 there is a simple, compactly generated, locally compact, totally disconnected group G, with flat-rk(G) = n and which is not linear.     

Structural and spectroscopic studies of silylated cyclo- and bicyclosilanes

A number of cyclo-and bicyclosilanes have been prepared and structurally characterized by X-ray crystallography and Raman spectroscopy. 1,1,4,4- and 1,1,3,3-tetrakis(trimethylsilyl)octamethylcyclohexasilanes were found to exhibit unusual twist- and twisted boat-conformations. The UV absorption properties of all compounds were studied and found to show absorption maxima red shifted compared to the parent compound dodecamethylcyclohexasilane. Dedicated to Prof. Mitsuo Kira on the occasion of his reception of the Wacker Silicon Award 2005 and in recongnition of his numerous outstanding achievements in organosilicon chemistry.     

Preparation,properties and X-ray cystal structures of complexes of 4,4-diethylmorpholinium with 2,5-dibromo- and 2,5-dichloro-7,7,8,8-tetracyano-p-quinodimethane : DEM(TCNQBr2)2 and DEM-TCNQCl2

4,4-Diethylmorpholinium forms a 1:2 complex with 2,5-dibromo-TCNQ and a 1:1 complex with 2,5-dichloro-TCNQ; both are insulators at room temperature, and their single crystal $\text{X}$-ray structures have been determined at 293 K.     

The observation of a large gauche preference when 2-fluoroethylamine and 2-fluoroethanol become protonated

The energies of the gauche and anti conformers of 2-fluoroethylamine, 2-fluoroethanol and their protonated analogues are calculated using density functional theory. Unlike the non protonated systems, the protonated systems show a strong gauche effect where the C-F and the C-(+)NH(3) or C-F and C-(+)OH(2) bonds are gauche rather than anti to each other. Single crystal X-ray diffraction studies of 2-fluoroethylammonium compounds identify the same conformational preference.     

Effect of included guest molecules on the normal state conductivity and superconductivity of beta''-(ET)(4)[(H(3)O)Ga(C(2)O(4))(3)].G (G = pyridine,nitrobenzene)

Normal state conductivity and superconductivity together with bulk magnetic susceptibility and magnetization measurements have been measured for two molecular charge-transfer salts: beta' '-(ET)4[(H3O)Ga(C2O4)3]G (ET = bis(ethylenedithio)tetrathiafulvalene, G = pyridine for compound I and nitrobenzene for compound II). With the exception of the included guest molecules (G) the crystal structures are almost identical. Both show minima in their electrical transport at 130 K for I and at 160 K for II, but at lower temperatures their behaviors differ markedly. The resistance of I reaches a maximum at 50 K with a further small peak at 2 K and possible superconductivity only below 2 K, whereas that of II increases continuously down to 7.5 K, where an abrupt transition to a superconducting state occurs.