Preparation and Eh--pH diagrams of Fe(II)--Fe(III) green rust compounds; hyperfine interaction characteristics and stoichiometry of hydroxy-chloride, -sulphate and -carbonate

Fe(II)--Fe(III) hydroxy-chloride, -sulphate and -carbonate were prepared by oxidation of a ferrous hydroxide precipitate in anion-containing aqueous solutions. The compounds are characterized by monitoring the redox potential E_h and the pH of stochiometric suspension vs time with the appropriate concentration ratios. X-ray diffraction allows us to characterize the crystal structure by distinguishing “green rust one” (GR1) from “green rust two” (GR2). Since green rusts (GRs) are of a pyroaurite-sjögrenite-like structure, i.e., consisting of intercalated foreign anions and water molecules in the interlayers between the brucite-like layers of Fe(OH)₂, their chemical formulae can be determined from the Mössbauer spectra. Three quadrupole doublets are observed: D₁ and D₂ correspond to a ferrous state with isomershift IS of about 1.27 mm s^-1 and quadrupole splittings QS of about 2.85 and 2.60 mm s^-1, respectively, whereas D₃ corresponds to a ferric state with IS and QS of about 0.4 mm s^-1. The hyperfine parameters of these doublets are similar from one green rust to another but their intensity ratios vary considerably. Finally, E_h and pH equilibrium diagrams of the Fe species in the presence of chloride, sulphate and carbonate anions contained within the water solution are drawn and the thermodynamic conditions of existence and degrees of oxidation of green rusts are discussed.     

Chemical composition and reaction analysis of single aerosol particles

In situ measurements of gas-liquid surface reactions of single aerosol microdroplets are presented. By means of optical levitation in combination with elastic (Mie) and inelastic (Raman) light scattering it is possible to get information on the chemistry of e.g. acid/base reactions as well as the physical behavior of single microparticles.     

Spin-trapped hydroxyl free radicals studied at low field by Field-Cycled Dynamic Nuclear Polarization

The technique of Field-Cycled Dynamic Nuclear Polarization (FC-DNP) involves the EPR irradiation of a free radical solution and the subsequent observation of the NMR signal, the experiment being carried out at a range of magnetic field strengths in order to measure the free radical’s EPR spectrum. In this work FC-DNP has been used to study the EPR spectrum of DMPO spin-trapped hydroxyl free radicals at magnetic field strengths between 0.5 mT and 13.0 mT (5–130 Gauss). The low-field EPR spectrum contains six separate EPR lines, in contrast to the well-known X-band spectrum where only four are seen. Knowledge of the spin-adduct’s EPR spectrum will be of use to workers involved in low-field EPR, especially those conducting biological or in-vivo spin-trapping experiments.     

Crystal field and magnetic properties of the tetragonal TbNi2Si2 compound

The magnetic properties of a TbNi₂Si₂ single crystal have been investigated experimentally by specific heat, anisotropy of the susceptibility and magnetization, and inelastic neutron scattering, leading to the determination of its fundamental coupling parameters. The lowest crystalline electric field states are two singlets close to each other, that explains the different magnetic structures evidenced in TbNi₂Si₂: an amplitude modulated structure, close to T _N , a simple antiferromagnetic one at low temperature and an antiphase one when an external magnetic field is applied along the c direction.     

Selective saturation and inversion of multiple resonances in high-resolution solid-state 13C experiments using slow spinning CP/MAS and tailored DANTE pulse sequences.

Taking advantage of the long 13C T1 values generally encountered in solids, selective saturation and inversion of more than one resonance in 13C CP/MAS experiments can be achieved by sequentially applying several DANTE pulse sequences centered at different transmitter frequency offsets. A new selective saturation pulse sequence is introduced composed of a series of 90 degrees DANTE sequences separated by interrupted decoupling periods during which the selected resonance is destroyed. Applications of this method, including the simplification of the measurement of the principal values of the 13C chemical shift tensor under slow MAS conditions, are described. The determination of the aromaticity of coal using a relatively slow MAS rate is also described.     

Enhancement of the backscattered intensity from fractal aggregates

Comparative measurements were conducted for the backscattered intensities of light from uniform random and fractal aggregated media. Different features are found for the backscattered intensity peak shapes. A crossover between the θ^1-D and θ^-2 dependences of the backscattered intensity occurs in the case of fractal aggregated medium, where D indicates the fractal dimension.     

Gain depletion due to amplified spontaneous emission in multi-pass laser amplifiers

Calculations of the effects of amplified spontaneous emission (ASE) in laser amplifiers designed to amplify sub-picosecond pulses are presented. A one-dimensional code is used with some simple approximations to account for aspect ratio variation in cases of cylindrical symmetry. Gain depletion due to ASE is compared for various multi-pass geometries. Optimisation for short pulse amplification of a telescopic, beam-expanding, 4-pass amplifier is considered.On leave from Electrotechnical Laboratory, Tsukuba, Ibaraki, Japan