On quadratic forms of height two and a theorem of Wadsworth

Let and be anisotropic quadratic forms over a field of characteristic not . Their function fields and are said to be equivalent (over ) if and are isotropic. We consider the case where and is divisible by an -fold Pfister form. We determine those forms for which becomes isotropic over if , and provide partial results for . These results imply that if and are equivalent and , then is similar to over . This together with already known results yields that if is of height and degree or , and if , then and are equivalent iff and are isomorphic over .

     

Hypothetical C(60) Metal-Cluster Fullerides and General Aspects of Tetrahedral Cluster Bonding

It is geometrically feasible to insert metal-metal-bonded M(4) tetrahedra and M(6) octahedra into the tetrahedral and octahedral holes, respectively, of the fcc C(60) lattice. The electronic structure of the hypothetical tetrahedral variants C(60)(M(4))(2), M = Rh, Co, is analyzed with approximate molecular orbital methods and band structure calculations. These compounds feature M-M and M-C(60) bonding and a variable degree of electron transfer to or from C(60). The C(60)(M(4))(2) phases should be metallic, but we have no way of predicting if they will be superconducting. A number of discrete molecular tetrahedral cluster compounds which serve as models for the solid state materials are analyzed. There is a clear indication that tetranuclear and even mononuclear Rh, Ir, and Co arene complexes should be relatively unstable.     

New hardware for radio frequency powered glow discharge spectroscopies and its capabilities for analytical applications

A new radio frequency (rf) hardware is developed for glow discharge spectroscopic methods. The resulting features and its capabilities for analytical applications are discussed. The electrical equipment developed allows to work as quickly, stably, reliably and easily as known from the direct current (dc) mode. Moreover, the rf power measurement has been improved. The hardware has been developed, optimised and tested for glow discharge optical emission spectroscopy (GDOES), but nevertheless it is possible to use it for all procedures applying glow discharge sources.     

Electronic Structure of [Ta(5)(NH)(4)Cl(17)](6-): A Cluster with a Distorted Square Pyramidal Ta(5) Core

We report approximate molecular orbital calculations on the [Ta(5)(NH)(4)Cl(17)](6-) cluster synthesized by Simon and Meyer. The cluster is based on a "flattened" square pyramid of tantalum atoms, basal bridging imides, and terminal chlorides. This cluster was of interest to us due to the unusual presence of imide ligands, the distorted nature of the metal core, and the possible resemblance to B(5)H(9). Our calculations indicate that metal-metal bonding is limited to Ta(apical)-Ta(basal) bonding, with no significant bonding between the basal metal atoms. The imide ligands, which bridge the base of the pyramid, were found to have a significant amount of capping character. The metal-metal bonding orbitals have some unusual features due to the pyramid's distortion. Additionally, the flattened nature of the pyramid leads to an interesting energy ordering of the metal-metal bonding orbitals.     

The Four-Connected Net in the CeCu(2) Structure and Its Ternary Derivatives. Its Electronic and Structural Properties

The crystallochemistry of and the bonding in the orthorhombic four-connected nets of BaIn(2) (CeCu(2) structure) and of CaPtSn (TiNiSi structure, a derivative of the CeCu(2) structure) are analyzed with approximate molecular orbital calculations. Following the Zintl concept, in BaIn(2) the In(-) ions are isoelectronic with group IV tin and should adopt a four-connected structure. In contrast to alpha-tin, which has a cubic diamond structure, the indium ions in BaIn(2) build up an orthorhombic three-dimensional four-connected net containing distorted tetrahedra and ladder polymers of four-membered rings. In the CeCu(2) structure (space group Imma) two bond angles in these distorted tetrahedra are fixed at 90 degrees. The four-connected net in the CeCu(2) structure is topologically related to the layers in black phosphorus (space group Cmca). In CaPtSn (TiNiSi structure) the orthorhombic four-connected net is formed by (PtSn)(2)(-) ions in an ordered arrangement. Calculations on BaIn(2) and CaPtSn show that the four-connected nets are increasingly stabilized as the valence electron count is increased from 16 to 30 valence electrons per 4 formula units. For more than 30e, the nets are destabilized due to filling of M-E antibonding states. Structural data obtained by precise single crystal investigations for the TiNiSi series CaPdIn (20e), CaPdSn (24e), CaPdSb (28e), and CaAgSb (32e), confirm the results of the extended Hückel calculations. We find an interesting and understandable angular asymmetry of the tetrahedral sites in these ternary compounds.     

Particle analysis of car exhaust by ETV-ICP-MS

Particulates of platinum group elements (Pt, Rh, Pd, Ir) emitted in automotive catalyst exhaust were measured down to the pg/m(3) level. Samples were taken from a standard type three-way catalyst equipped gasoline engine, running on a computer controlled dynamometer. Particulates in catalyzed car exhaust were sampled fractionated according to size by using the cascade impactor with separate targets mounted underneath each nozzle. The targets, small flat discs made of pure graphite, were subsequently analyzed by ETV-ICP-MS without any preparatory steps.     

Vesicle phases from N-methyl-N-alkanoylglucamin and various co-surfactants

We have studied the phase behavior of N-methyl-N-alkanoylglucamin (GA) in water and the influence of various additives on the phases of GA. We find that GA forms a large L₁-phase that extends up to 60 wt.% of surfactant. The viscosity in this phase increases with increasing concentration and decreasing temperature. When solutions are cooled down below the Krafft-temperature (21–28 °C) T_k the samples transform into clear gels that are stable for several months. The transformation of the gel to the L₁-phase proceeds in two separate steps. Acid–base titration experiments show that the commercially produced GA is not a pure well defined compound but contains about 10% of an anionic surfactant, most likely dodecanoic acid. Solutions of GA can be continuously mixed with the anionic surfactant sodiumdodecylsulfate (SDS) or sodiumdodecylethoxysulfate (SDES) to clear and low viscous phases. Solutions of GA mixed with increasing amount of cationic surfactant tetradecyltrimethylamoniumbromide (TTABr) transform first into two phase systems and then again into low viscous single phases. The influence of several chemically different co-surfactants like n-alcohols, octanoic acid, oleic acid, 2-ethylhexylmonoglyceride (EHMG) and oleylmonoglyceride on the phase behavior of phases with 5% GA has been studied. With increasing mole fraction of the co-surfactants the well-known sequence of phases is observed, namely a L₁-phase, a two phase region L₁/L- and a L-phase. However, the properties of the L-phase for the different systems are very different. For samples with octanol the L-phase is an optically isotropic, transparent, highly viscoelastic gel. Without shear the gel like phase shows no birefringence. FF-TEM micrographs show that it consists of rather monodisperse, unilamellar vesicles with a diameter of about 500 Å. The L-phases for the other co-surfactants are turbid and have a rather low viscosity. They also contain vesicles but with a rather broad size distribution ranging from 200 to 1000 Å. For the same co-surfactant/surfactant ratio the various systems differ also in their conductivity. For some systems the conductivity is only about 20% lower than in the corresponding L₁-phase while in other systems the difference is more than a factor two. These results are an indication that small uni-lamellar vesicles contain more ionic groups at the outside than on the inside of the bilayer and that some systems are composed of uni-lamellar vesicles while others are composed of multilamellar vesicles (onions).     

Novel [2 + 2] photocycloaddition-induced rearrangement of bichromophoric naphthalene-tethered resorcinol ethers

The first examples of sequential photocycloaddition-rearrangement reactions of naphthalene-tethered resorcinol ethers are described. Bichromophoric aromatic compounds with naphthalene and resorcinol ether moieties were irradiated in the presence/absence of a small amount of acid to give the corresponding cycloaddition-rearrangement products. From the determination of quantum yields, steady-state fluorescence spectral studies, and fluorescence lifetime measurements, the mechanism of this novel photoinduced multistep reaction was elucidated to involve the initial intramolecular exciplex formation, followed by the intramolecular [2 + 2] photocycloaddition between the two aromatic rings and the subsequent acid-catalyzed skeletal rearrangement of the resulting cyclobutane derivative leading to the final products.