Characterization of core-shell nanoparticles by small angle neutron scattering

The Ni₃Si-type nanoparticles dispersed in a mixture of H₂O/D₂O were characterised by SANS using the contrast variation method. The existence of a core-shell structure in the nanoparticles with a Ni₃Si(Al) core and amorphous SiO_x shell is confirmed by the SANS measurements. The nanoparticles were produced by extracting precipitates from a bulk Ni-13.3Si-2Al ( at. %) alloy using electrochemical phase separation technique and were pre-characterised by X-ray diffraction and transmission electron microscopy. By comparing the precipitate morphology in the Ni-Si-Al alloy with the extracted nanoparticles in the SANS measurements, it is clearly established that the precipitates shape and size are unaffected by the extraction process and that the amorphous shell forms on top of the particle core. However, the present measurement could not confirm or exclude the presence of H atoms in the shell structure. PACS 61.12.Ex; 61.12.-q; 61.46.Df; 61.82.Rx     

Vibrational relaxation and dephasing of Rb2 attached to helium nanodroplets

The vibrational wave-packet dynamics of diatomic rubidium molecules (Rb(2)) in triplet states formed on the surface of superfluid helium nanodroplets is investigated both experimentally and theoretically. Detailed comparison of experimental femtosecond pump-probe spectra with dissipative quantum dynamics simulations reveals that vibrational relaxation is the main source of dephasing. The rate constant for vibrational relaxation in the first excited triplet state 1(3)Σ(g)+ is found to be constant γ ≈ 0.5 ns(-1) for the lowest vibrational levels v ? 15 and to increase sharply when exciting to higher energies.     

Magnetic anisotropy and low-frequency dielectric response of weak ferromagnetic phase in κ-(BEDT-TTF)2Cu[N(CN)2]Cl, where BEDT-TTF is Bis(ethylenedithio)tetrathiafulvalene

We report a detailed characterization of the magnetism and AC transport in single crystals of the organic conductor -(BEDT-TTF)₂Cu[N(CN)₂]Cl by means of magnetic anisotropy measurements and low-frequency dielectric spectroscopy. Magnetic anisotropy obeys Curie-Weiss law with negative Curie-Weiss temperature in the temperature range 300 K-70 K. An antiferromagnetic transition with concomitant canted antiferromagnetic state is established at 22 K. A large hysteresis in the spin-flop transition and magnetic field reversal of the weak ferromagnetic magnetization are documented for the first time. A broad dielectric relaxation mode of moderate strength () emerges at 32 K, and weakens with temperature. The mean relaxation time, much larger than that expected for single-particle excitations, is thermally activated in a manner similar to the DC conductivity and saturates below 22 K. These features suggest the origin of the broad relaxation as an intrinsic property of the weak ferromagnetic ground state. We propose a charged domain wall in a random ferromagnetic domain structure as the relaxation entity. We argue that the observed features might be well described if Dzyaloshinsky-Moriya interaction is taken into account. A Debye relaxation with similar temperature dependence was also observed and seems to be related to an additional ferromagnetic-like, most probably, field-induced phase. We tentatively associate this phase, whose tiny contribution was sample dependent, with a Cu²⁺ magnetic subsystem. Received 15 June 1998 and Received in final form 1 February 1999     

Studies in stereoselective [2+2]-cycloadditions with dichloroketene

During the investigation of the reaction of dichloroketene with cyclic enoxy-lactones and acyclic enoxy-ester substrates it was found that only the acylic variants effectively participated in the [2+2]-cycloaddition. Although a complete understanding of the reasons for this are lacking, molecular mechanics calculations do suggest that an out of plane twist of the cabonyl group in the acyclic compounds may be partially responsible. After screening a variety of chiral auxiliaries it was found that useful levels of diastereoselectivity (2.6-10.8:1) could be obtained in this cycloaddition reaction when (R)-2,2-diphenylcyclopentanol was used as the chiral auxiliary.     

Untersuchung von Kartoffeln, Gerste und Malz

Ohne Zusammenfassung     

Structural, volumetric, and thermodynamic characterization of a micellar sphere-to-rod transition

The thermotropic sphere-to-rod transition of nonionic surfactants was characterized in terms of a large set of parameters: the transition temperature and width, the partial volume, coefficient of thermal volume expansion, enthalpy, isobaric heat capacity, and structural parameters, such as radius of gyration and hydrodynamic radius. Data were recorded as a function of concentration of surfactants in H2O and in D2O. To this end, pressure perturbation calorimetry (PPC), small angle neutron scattering (SANS), dynamic light scattering (DLS), differential scanning calorimetry (DSC), and isothermal titration calorimetry (ITC) were applied in a study of aqueous solutions containing myristyl, tridecyl, and lauryl maltoside and heptaethyleneglycoltetradecyl ether (C14EO7). Small changes in the thermodynamic and volumetric parameters (e.g., the partial volume change is approximately +2 per thousand) are discussed in detail as the result of three effects governing the transition. (i) Reduction of the water accessible hydrophobic surface area (ASA(ap)) drives the transition. (ii) Shrinking in headgroup size by thermal dehydration triggers the transition. (iii) Hypothesized gradual ordering of the chains may control the effect of chain length on the transition.     

On the stoichiometry of the organic metal bis(ethylenedioxy)-tetrathiafulvalene chloride

We report on Shubnikov-de Haas and de Haas-van Alphen measurements of an organic metal based on the molecular donor bis(ethylenedioxy)-tetrathiavulvalene (= BEDO-TTF) and the anion Cl^- with H₂O molecules. The observed single oscillation frequency perfectly follows the two-dimensional dependence with T. The Fermi-surface area of of the first Brillouin zone proves a quarter-filled band, i.e., a 2:1 stoichiometry of the BEDO-TTF donor with respect to the anion. The apparent discrepancy to X-ray data which give a 1:1 ratio between BEDO-TTF and Cl^- is understood by replacement of H₂O molecules with (H₃O)⁺ ions. The proposed stoichiometry therefore is (BEDO-TTF)₂ ⁺(H₅O₂)⁺(Cl^-)₂. The cyclotron effective mass is when deduced from the temperature dependence of the fundamental oscillation amplitude, but strongly reduced when extracted from higher harmonics. This and the strong harmonic content of the oscillations signals an influence of the two-dimensional electronic structure and can be qualitatively understood by applying the concept of magnetic interaction to the effect of the oscillatory chemical potential. Received: 16 April 1998 / Revised: 7 July 1998 / Accepted: 9 July 1998