quite difficult. It has been shown that the width of the filter window is inversely proportional to the degrees of freedom allowable in the subsequent 2 34minimization routine. Practically, then, one must perform the minimization on the unfiltered spectrum leading to the undesirable consequence of minimization in many parameters of a maximum likelihood estimator that is large and, hence, relatively insensitive to the small changes in parameters that would differentiate between models. ConclusionsThe surface EXAFS of underpotentially deposited silver on gold (111) films on mica was studied with the electrode under potential control. It was revealed that both gold and oxygen are present as backscatterers in the first coordination shell of silver. It was estimated that the bond lengths to gold and oxygen were 2.75 ± 0.05 and 2.42 ± 0.05 Á, respectively, and the respective coordination numbers were 3 and 1. A model consistent with these findings is one where the silver atoms sit on 3-fold sites on the gold surface and have oxygen from water or electrolyte bound at a well-defined distance. This model is qualitatively the same as that proposed for the Cu UPD layer on gold (111) electrodes.

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The cold neutron imaging and diffraction instrument IMAT at the second target station of the pulsed neutron source ISIS is currently being commissioned and prepared for user operation. IMAT will enable white-beam neutron radiography and tomography. One of the benefits of operating on a pulsed source is to determine the neutron energy via a time of flight measurement, thus enabling energy-selective and energy-dispersive neutron imaging, for maximizing image contrasts between given materials and for mapping structure and microstructure properties. We survey the hardware and software components for data collection and image analysis on IMAT, and provide a step-by-step procedure for operating the instrument for energy-dispersive imaging using a two-phase metal test object as an example.

It was observed that when polarized by an intense electric field, water is able to self-arrange into macroscopic cylindrical wires that can hang up and remain floating against gravity. This phenomenon is now known as a ‘water bridge’. Several attempts have been made to give an explanation of this apparently unusual behaviour of water. A number of experiments have been performed with the aim of probing any possible structural change of bulk water, after application of the electric field. None of the available findings appear conclusive at the moment.Here we report the results of the first Raman scattering experiment on floating water bridges. The inter-molecular OH-stretching band has been investigated and the results have been compared with those from bulk water. Some changes in the scattering profiles after application of the electric field are shown to have a structural origin. The bridges have been obtained, for the first time, in a vertical geometry and under application of an alternating field. The adopted geometry has allowed us to reveal a clear asymmetry between opposite direct current biasing, which can be related to the nature of the charge carriers.

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Aqueous solutions of poly(ethylene glycol) (PEG) of mean molecular mass of 600 g/mol (PEG600) are investigated by Brillouin scattering technique. At high PEG content, a relaxation phenomenon is observed, which is related to a local rearrangement of the polymer structure where the interaction, via hydrogen bonding, with the solvent molecules plays a role. The obtained values of the relaxation times match the literature data very well for a fast relaxation time revealed by dielectric relaxation measurements in very similar mixtures. The calculated concentration behaviors of the excess adiabatic compressibility turns out in good agreement with the previous findings from ultrasonic measurements at 3 MHz. The observed minimum in the adiabatic compressibility is interpreted as the result of the interaction between water and the EO units of the PEG chain, which results in a structure tighter then that typical of bulk water and of pure PEG600. Such a hypothesis is supported by the observation that volume fraction value of about 0.3 coincides with the concentration value at which full hydration of EO units takes place. The observation that at the same concentration, the polymer coils start to overlap each other further supports the idea that the adiabatic compressibility behavior is monitoring the structural evolution of the mixture. However, similar results are obtained for largely different binary mixture which suggests caution in taking this conclusion too literally. In particular, the hypothesis that the occurrence of an extreme in the excess adiabatic compressibility could be simply originated by statistical effects and that further work is required for disentangling entropic contribution from effects of hetero-association and self-aggregation of one or both the components.

We present results of a Brillouin scattering experiment on solutions of poly(ethylene glycol) of mean molecular mass 600 g/mol (PEG600) in CCl4. The relaxation process detected has been assigned to conformational rearrangements of the polymeric chains, triggered by reorientation of the side groups. The concentration dependencies of the hypersound velocity and normalized absorption are compared against the indications from several models proposed in the literature. The concentration evolution of the system is described in terms of two distinct regimes. At high polymer content, the system is dominated by the structure of the dense polymer, where polymer-polymer interactions, together with excluded volume effects, induce the existence of a preferred local arrangement resulting in a narrow distribution of the relaxation times, with the average value of the relaxation time following a simple Arrhenius temperature dependence. As the concentration decreases, the original structure of the hydrogen bonded polymer network is destroyed, and a number of different local configuration coexist, giving rise to a wider distribution of relaxation times or to a multiple relaxation. At low concentrations, the experimental data are well fitted assuming a Vogel-Fulker-Tammon behavior for the average relaxation time. In addition, the observed deviation from the ideal behavior for the refractive index and the density suggests that CCl4 does not behave as an inert solvent, and due to polarization effects, it can develop local hetero-associated structures via electrostatic interaction with the O-H end groups of the polymeric chains. The hypothesis has been successfully tested by fitting the concentration behavior of the hypersonic velocity to a recent three-component model, suitable to describe the concentration dependence of sound velocity in moderately interacting fluids. The indication of the model furnishes a very high value for the association constant of the PEG600, confirming the literature indication that, in polymeric systems capable of developing long liner aggregates via hydrogen bonding interaction, the Brillouin probe is insensitive to the true length of the polymeric chains. The Brillouin scattering experiment just sees an effective hydrogen bonded aggregate that is huge relative to the length of the single polymeric chain and becomes sensitive only to the density fluctuations of the local segmental motions.