Messung der Elektrodiffusion. Einfluß der Elektroosmose auf die Diffusion

Ohne Zusammenfassung     

Ordering and diffuse phase transitions in Pb(Sc0.5Ta0.5)O3 ceramics

The ordering of the Sc³⁺ and Ta⁵⁺ ions in Pb (Sc_0.5Ta_0.5) O₃ can be varied by proper heat treatments (1000–1500°C). The ferroelectric → paraelectric transition is strongly influenced by this ordering. With decreasing order parameter Ω the phase transition becomes more diffuse and a number of properties show strong changes.     

Mixed-symmetry states in the neutron-proton interacting boson model

States of mixed proton-neutron symmetry are investigated in different dynamical symmetries of the interacting boson model. We discuss in each of the limits the energy spectrum, the wave functions and the B(M1; 0₁⁺ → 1 _1⁺) values. We also study three classes of transitional nuclei namely the Pd nuclei [U(5) → O(6)], the Sm nuclei [U(5) → SU(3)] and the Pt nuclei [O(6) → SU(3)] with respect to the energy of the lowest non-symmetric J^π = 1⁺, 3⁺ levels as well as the M1 and M3 strengths for exciting these levels from the ground state. For ⁹⁸Pd we compare this calculation with a shell-model calculation. Finally, we adress the problem of the mixing of the non-symmetric J^π = 1⁺ state with nearby hexadecapole (g-boson) configurations.     

Polymerization of propadiene. IV. Kinetics and mechanism of polymerization under the influence of rhodium(I) complexes

The kinetics and mechanisms of propadiene polymerization under the influence of [Rh(CO)₂Cl]₂, Rh(CO)₂P(C₆H₅)₃Cl, Rh(CO)₃Cl are reported. The reaction rates are first-order in Rh(CO)₂P(C₆H₅)₃Cl and Rh(CO)₃Cl and half-order in [Rh(CO)₂Cl]₂. They are second-order in the substrate for Rh(CO)₃Cl and [Rh(CO)₂Cl]₂ and first-order for Rh(CO)₂P(C₆H₅)₃Cl. The data are interpreted in terms of a common intermediate mechanism. The formation of this common intermediate is the rate-determining step. A solvent effect is also discussed.     

Cooperative Effects in π-Ligand Bridged Dinuclear Complexes. XII [1]. Heterodinuclear Electron Poor μ-Cyclooctatetraene Complexes with CrFe-and CrCo-Combinations

The synfacial heterodinuclear μ-Cot complexes (Cot = cyclooctatetraene) [(CpCr) (CpM)]μ-Cot (Cp = cyclopentadienyl; M ? Fe, 3 ; M ? Co, 4 ) are formed in a thermal reaction of the mononuclear mixed sandwich compound CpCr(n⁶-Cot) and CpML_n [M ? Fe, L_n = benzene (Bz); M ? Co, L_n = (C₂H₄)₂]. 3 possesses two unpaired electrons whereas 4 has only one unpaired electron and is ESR active. From the molecular structure of 3 and from the ESR data of 4 it can be deduced that the unpaired electrons are localized at the Cr centers predominantly forcing a close electronical relation between the heterodinuclear compounds 3 and 4 and the mononuclear sandwich complexes chromocene and CpCrBz, respectively.     

Tuning the selectivity of ruthenium nanoscale catalysts with functionalised ionic liquids: Hydrogenation of nitriles

Ruthenium nanoparticles prepared in nitrile-functionalised ionic liquids (ILs) display unusual selectivities toward the hydrogenation of nitrile containing aromatic compounds. In particular, a selective catalytic hydrogenative coupling of nitriles was observed. In this transformation, nitrile groups are exclusively hydrogenated in the presence of arenes, which are typically hydrogenated by ruthenium nanoparticles in non-functionalised ILs. The catalyst material was characterised by means of TEM and EDS analysis. Furthermore, molecular species formed during the catalytic process were characterised by MS-analysis of the gaseous phase and the ionic liquid phase by ESI/MS Q-TOF.     

Uniform molecular analysis using femtosecond laser mass spectrometry

The potential of femtosecond laser time-of-flight mass spectrometry (FLMS) for uniform quantitative analysis of molecules has been investigated. Various samples of molecular gases and vapours have been studied, using ultra-fast ( approximately 50 fs) laser pulses with very high intensity (up to 1.6 x 10(16) Wcm(-2)) for non-resonant multiphoton ionisation/tunnel ionisation. Some of these molecules have high ionisation potentials, requiring up to ten photons for non-resonant ionisation. The relative sensitivity factors (RSF) have been determined as a function of the laser intensity and it has been demonstrated that for molecules with very different masses and ionisation potentials, uniform ionisation has been achieved at the highest laser intensities. Quantitative laser mass spectrometry of molecules is therefore a distinct possibility. Copyright 1999 John Wiley & Sons, Ltd.     

Gas-phase deprotonation of arylalkylamines. A collision-induced dissociation study

The collision-induced dissociation (CID) of deprotonated arylalkylamines of general formula R(1)C(6)H(4)CHR(2)CH(2)NR(3)(2) (where R(1) = H, OH, F or NO(2); R(2) = H or OH; R(3) = H or CH(3)) generated by negative chemical ionization with H(2)O and D(2)O as ionizing reagents, is discussed. The negative chemical ionization mass spectra show that, in the absence of a hydroxy group in the aromatic ring, deprotonation takes place at the benzylic position whereas the proton is lost from the OH group when present. The nitro compound forms only M(-.) ions. The CID spectra of the deprotonated molecules show that fragmentations are strongly dependent on the structural features of the molecules, namely the presence or absence of substituents in the aromatic ring or aliphatic chain. Copyright 1999 John Wiley & Sons, Ltd.