Resolution of the A- and B-site hyperfine fields of the spinel system Mg1+t Fe2(1−t ) Ti t O4 in the spin-glass-like state

Spectra for three members of the spinel system Mg_1+t Fe_2(1−t)Ti _t O₄, witht=0.5, 0.6 and 0.7, all showing re-entrant spin-glass-like behavior, were collected at temperatures down to 1.6 K and decomposed in A- and B-site components, both having a broad distribution of hyperfine fields. The numerical results suggest a more pronounced spin canting on A sites as compared to B sites. From spectra recorded at 4.2 K in an applied field of 6 T, and analysed with a sum of two bi-dimensional distributions of hyperfine fields and canting angles, the existence of reversed A-site spins is evidenced. The number of such spins increases with increasing magnetic dilution. Senior Research Associate at the National Fund for Scientific Research, Belgium     

Femtosecond midinfrared study of aggregation behavior in aqueous solutions of amphiphilic molecules

We study the spectral and orientational dynamics of HDO molecules in aqueous solutions of different concentrations of tertiary butyl alcohol (TBA) and trimethylamine-N-oxide (TMAO). The spectral dynamics is investigated with femtosecond two-dimensional infrared spectroscopy of the O-H stretch vibration of HDO:D(2)O, and the orientational dynamics is studied with femtosecond polarization-resolved pump-probe spectroscopy of the O-D stretch vibration of HDO:H(2)O. Both the spectral and orientational dynamics are observed to show bimodal behavior: part of the water molecules shows spectral and orientational dynamics similar to bulk liquid water and part of the water molecules displays a much slower dynamics. For low solute concentrations, the latter fraction of slow water increases linearly as a function of solute molality, indicating that the slow water is contained in the solvation shells of TBA and TMAO. At higher concentrations, the fraction of slow water saturates. The saturation behavior is much stronger for TBA solutions than for TMAO solutions, indicating the aggregation of the TBA molecules.     

Potentiometric determination of coextraction constants of potassium salts in ion-selective electrodes utilizing a nitrobenzene liquid membrane phase

A theoretical treatment of potentiometric data is applied to calculate coextraction constants (K_IA) for three potassium salts from water into a liquid nitrobenzene phase. The experiment involves treating nitrobenzene as a membrane and contacting it with two aqueous solutions of different ion activities. In the presence of either a cation or anion exchanger, the ratio of activities of ions in the two aqueous phases gives rise to a potential difference across the membrane that depends upon the nature and charge of the counter ion of the ion-exchanger in excess. Here, the cation exchanger was chosen to be potassium tetrakis(4-chlorophenyl)borate (KTpClPB) and the anion exchanger was tetradodecylammonium chloride (TDDACl). TDDACl was incrementally added to the nitrobenzene phase containing a fixed concentration of KTpClPB, and the corresponding emf was recorded as a function of concentration of TDDACl. The membrane changes from one with cation exchanger properties (excess KTpClPB) to one with anion exchanger properties (excess TDDACl). The potential difference and shape of the titration curve can be predicted by theory based on the phase boundary potential model. Log(K_IA) values calculated for KCl, KNO₃ and KClO₄ in nitrobenzene were found as: −10.53 (± 0.09), −8.16 (± 0.05) and −5.63 (± 0.03) respectively, in accordance with the Hofmeister series of lipophilicity, and similar to those observed in PVC membranes containing other plasticizers. The method presented here offers the advantage over other methods to calculate K_IA, in that it is relatively experimentally simple without compromising the accuracy of the calculated coextraction constants. The ability to titrate directly into the liquid membrane phase affords a higher precision compared to the preparation of a series of PVC/plasticizer membranes with different compositions.     

Light-Front Singularities

Calculations in light-front quantization are sometimes found to lead to singularities that are not present in the corresponding manifestly covariant treatment. We give some examples that were found in the framework of perturbation theory, but must also occur in nonperturbative calculations. In the case of anomalies, regularization-scheme dependences were found that not only occur between the light-front approach and manifestly covariant calculations, but also among the latter ones.     

Hyperfine interactions of aluminum-substituted goethites in external magnetic fields

Six goethite samples α(Fe, Al)OOH prepared by a similar synthetic method but varying in Al substitution from 0 to 31 mole percent, have been examined by Mössbauer spectroscopy at ≌ 4 K in an external field of 6 T. The resulting spectra have been fitted by two methods: first a simplified model consisting of three distributions of magnetic fields (parallel, perpendicular and antiparallel orientations of internal and external field) and second, a model-independent bi-dimensional distribution of both the internal hyperfine field and the orientation angle ? with the external field. Both fitting methods show that the angular distribution of spins is not random in the case of high Al substitution, but canted towards an antiparallel orientation (?>90°).     

Mössbauer study of small-particle maghemite

Two small-particle maghemite (λ-Fe₂O₃) samples have been investigated with the Mössbauer effect. From the results of the model-independent hyperfine-field distribution fits some characteristic temperature-dependent parameters have been obtained. The spectra at the lowest temperatures could be fitted with two strongly overlapping hyperfine-field distributions with different isomer shifts. Spectra in applied magnetic fields ranging from 40 to 60 kOe, and at 4.2 K showed non vanishing Δm ₁=0 absorption lines. The hyperfine-field distribution and canting-angle distribution method for fitting these spectra did not yield reasonable results. Therefore, a bi-dimensional hyperfine-field-canting-angle distribution has been applied, and was found to reproduce the experimental line shapes with remarkable adequacy. The resulting distribution profiles revealed a linear correlation between H_hf and the angle between the magnetic moments and the external field.     

Quantitative planar Raman imaging through a spectrograph: visualisation of a supersonic wedge flow

Planar Raman imaging through a spectrograph is demonstrated as a diagnostic tool for quantitative flow visualisation of internal supersonic wedge flow. A dedicated Bayesian deconvolution filter is used to remove the spectral structure that is introduced by the spectrograph. The 2D density field is determined with ca. 10% precision using average images over 6,000 laser pulses, down to 0.5 mm from the surface of the wedge. Direct interpretations of Raman intensities provide more precise density data than indirect interpretations based on shock geometry in 2D inviscid flow.

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Vibrational dynamics of the bending mode of water interacting with ions

We studied the vibrational relaxation dynamics of the bending mode (ν(2)) of the H(2)O water molecules in the presence of different salts (LiCl, LiBr, LiI, NaI, CsI, NaClO(4), and NaBF(4)). The linear and nonlinear spectra of the bending mode show distinct responses of water molecules hydrating the anions. We observe that the bending mode of water molecules that are hydrogen-bonded to an anion exhibits much slower relaxation rates (T(1)~1ps) than water molecules that are hydrogen-bonded to other water molecules (T(1)=400 fs). We find that the effect of the anion on the absorption spectrum and relaxation time constant of the water bending mode is not only determined by the strength of the hydrogen-bond interaction but also by the shape of the anion.     

Capillary Stokes drift: a new driving mechanism for mixing in AC-electrowetting

We studied the flow fields generated inside sessile drops that oscillate periodically between states of high and low contact angle under the influence of alternating electric fields of variable frequency and amplitude. Following the motion of dye patches, we show that the number of oscillation cycles required to achieve mixing scales logarithmically with the Péclet number as expected for chaotic mixing. High speed movies reveal an asymmetry of the drop shape between the spreading and receding phase of the oscillations. This results in net internal flow fields that we characterize by tracing the motion of colloidal seed particles. The strength and frequency dependence of the flow are explained in terms of Stokes drift driven by capillary waves that emanate from the oscillating contact line.