The CeO(2)(+) Cation: Gas-Phase Reactivity and Electronic Structure

"Bare" CeO(2)(+) ions can be prepared in the gas phase by consecutive oxidation of Ce(+) with O(2) and NO(2). The ability to activate saturated and unsaturated hydrocarbons is investigated by use of Fourier-transform ion cyclotron resonance mass spectrometry. In the reactions of CeO(2)(+) with linear and branched alkanes C-H bond activation is observed almost exclusively. In contrast, both oxygen-atom transfer and C-H bond activation processes occur when thermalized CeO(2)(+) cations react with simple alkenes and aromatic compounds. C-C bond activation is not observed at all. Insight into the structural and electronic properties of neutral CeO(2) and cationic CeO(2)(+) is provided by means of quasirelativistic density-functional and ab initio pseudopotential calculations. They reveal a (2)Sigma(u)(+) ground state for CeO(2)(+) which is best described as a linear cerium dioxide with a resonating pi bond. Finally, we discuss the influence of oxo ligands on the chemistry of the cationic CeO(n)()(+) (n = 0-2) species toward hydrocarbons.     

Etorphine‐Related Ferrocenyl‐Substituted Morphinan Alkaloids

The two diastereoisomeric ferrocenyl‐substituted orvinols 2 and 3 were prepared. The modified alkaloids are still able to interact with opioid receptors (see Table). The ferrocene moiety allows highly selective and sensitive electrochemical detection. The X‐ray crystal structure of the major isomer 2 was determined. The combination of a metallocene and a morphinan alkaloid holds promise for useful antitumor activity.     

Antisymmetry and analytic structure in the spectrum of a uniform Fréchet algebra

Let M be a C-smooth submanifold of a domain GCⁿ. Denote by 0(M) the algebra of germs of holomorphic functions on M, that is, each f0(M) is holomorphic in some neighbourhood of M, the neighbourhood dependent of f. Now define A(M) as the closure of 0(M) with respect to the topology of compact convergence on M.If M coincides with A(M), the spectrum of A(M), we give a necessary and sufficient condition for A(M) such that M is a complex manifold.     

Ebene Äquiforme Zwangläufe im Grossen II

Im ersten Teil dieser Arbeit¹ wurden die orientierten Flächeninhalte der Punktbahnen ebener äquiformer Zwangläufe studiert und einige Anwendungen der erzielten Resultate angeführt. Der vorliegende zweite Teil beschäftigt sich - unter Beibehaltung der Bezeichnungen, der Numerierung der Abschnitte, Sätze usw. - einerseits mit Geradenhüllbahnen, andererseits mit globalen Eigenschaften spezieller äquiformer Zwangläufe, und zwar mit der äquiformen Bewegung der Krümmungsstrecken einer ebenen Kurve, mit äquiformen Konchoiden-bewegungen und mit der äquiformen Bewegung der Durchmesser eines beschränkten konvexen Bereichs. Beim Studium der durch formale Integration gewonnenen, vorzeichenbehafteten “Längen” der Geradenhüllbahnen wurden zur Interpretation des Vorzeichens orientierte Geraden des Gangsystems betrachtet. Dieser anscheinend notwendige Übergang zu Speeren wurde bislang bei der Formulierung von Holditch-Sätzen über Längen von Geradenhüllbahnen (vgl.[11],[39]) nicht beachtet. Wie schon im ersten Teil gestatten die Ergebnisse eine Anwendung in der globalen euklidischen n-Lagentheorie sowie auf nichtgeschlossene euklidische Zwangläufe.     

CO laser stabilization using the optogalvanic Lamb-dip

Frequency stabilization of the CO laser using a CO lamb-dip is achieved in the range from 5.0–6.3 m. The CO saturation signal is obtained from a low-pressure discharge in absorption and is detected using optogalvanic, detection. The frequency stability and reproducibility has been verified to be better than 100 kHz; this is an improvement of more than one order of magnitude compared with locking techniques using CO laser gain profiles.Alexander von Humboldt Awardee from National Bureau of Standards, Boulder, Colorado, USA     

Analysis of the 3-dimensional electron distribution in silicon using directional Compton profile measurements

A method of reconstructing the electron momentum density (p), and its Fourier transform,B(t), from a series of directional Compton profiles is described. It is based on a double Fourier inversion technique and an expansion in lattice harmonic functions. The effect of random errors has been analysed, and the implications for the data collection discussed. We have used the reconstruction technique to obtain (p) andB(t) for silicon from six directional Compton profiles measured with 412 KeV gamma-radiation. The experimental result is in good agreement with earlier measurements and with available solid state theories. A recent Wannier function calculation for silicon using orthogonalised bond orbitals provides a useful tool for identifying the physical origins of the observed anisotropies. A comparison between the information presented in position and momentum space shows that the ease of interpretation depends upon the degree to which the various interactions give rise to localised features in each representation.