Very low sound velocities in iron-rich (Mg,Fe)O: Implications for the core-mantle boundary region

The sound velocities of (Mg_(.16)Fe_(.84))O have been measured to 121 GPa at ambient temperature using nuclear resonant inelastic x-ray scattering. The effect of electronic environment of the iron sites on the sound velocities were tracked in situ using synchrotron Mössbauer spectroscopy. We found the sound velocities of (Mg_(.16)Fe_(.84))O to be much lower than those in other presumed mantle phases at similar conditions, most notably at very high pressures. Conservative estimates of the effect of temperature and dilution on aggregate sound velocities show that only a small amount of iron-rich (Mg,Fe)O can greatly reduce the average sound velocity of an assemblage. We propose that iron-rich (Mg,Fe)O be a source of ultra-low velocity zones. Other properties of this phase, such as enhanced density and dynamic stability, strongly support the presence of iron-rich (Mg,Fe)O in localized patches above the core-mantle boundary

Phonon density of states and compression behavior in iron sulfide under pressure

We report the partial phonon densities of states (DOS) of iron sulfide, a possible component of the rocky planet's core, measured by the Fe-57 nuclear resonant inelastic x-ray scattering and calculate the total phonon DOS under pressure. From the phonon DOS, we drive thermodynamic parameters. A comparison of the observed and estimated compressibilities makes it clear that there is a large pure electronic contribution in the observed compressibility in the metallic state. Our results present the observation of thermodynamic parameters of iron sulfide with the low-spin state of an Fe2+ ion at the high density, which is similar to the condition of the Martian core

Phonons in Nanocrystalline 57Fe

We measured the phonon density of states (DOS) of nanocrystalline Fe by resonant inelastic nuclear γ-ray scattering. The nanophase material shows large distortions in its phonon DOS. We attribute the high energy distortion to lifetime broadening. A damped harmonic oscillator model for the phonons provides a low quality factor, Qu, averaging about 5, but the longitudinal modes may have been broadened most. The nanocrystalline Fe also shows an enhancement in its phonon DOS at energies below 15 meV. The difference in vibrational entropy of the bulk and nanocrystalline Fe was small, owing to competing changes in the nanocrystalline phonon DOS at low and high energies

Local Chemical Environments and the Phonon Partial Densities of States of 57Fe in 57Fe3Al

Inelastic nuclear resonant scattering spectra were measured on alloys of Fe3Al that were chemically disordered, partially ordered, and D03 ordered. The features in the phonon partial density of states of 57Fe were found to change systematically with chemical short-range order in the alloy. Changes in the phonon partial density of states were modeled successfully by assigning vibrational spectra to 57Fe atoms in different first-nearest-neighbor chemical environments

Measuring velocity of sound with nuclear resonant inelastic x-ray scattering

Nuclear resonant inelastic x-ray scattering is used to measure the projected partial phonon density of states of materials. A relationship is derived between the low-energy part of this frequency distribution function and the sound velocity of materials. Our derivation is valid for harmonic solids with Debye-like low-frequency dynamics. This method of sound velocity determination is applied to elemental, composite, and impurity samples which are representative of a wide variety of both crystalline and noncrystalline materials. Advantages and limitations of this method are elucidated

Atom clusters and vibrational excitations in chemically-disordered Pt357Fe

Inelastic nuclear resonant scattering spectra of Fe-57 atoms were measured on crystalline alloys of Pt3Fe-57 that were chemically disordered, partially ordered, and L1(2) ordered. Phonon partial density of states curves for Fe-57 were obtained from these spectra. Upon disordering, about 10% of the spectral intensity underwent a distinct shift from 25 to 19 meV. This change in optical modes accounted for most of the change of the vibrational entropy of disordering contributed by Fe atoms, which was (+0.10 +/- 0.03) k(B) (Fe atom)(-1). Prospects for parametrizing the vibrational entropy with low-order cluster variables were assessed. To calculate the difference in vibrational entropy of the disordered and ordered alloys, the clusters must be large enough to account for the abundances of several of the atom configurations of the first-nearest-neighbor shell about the Fe-57 atoms

Heterogeneous electron-transfer kinetics with synchrotron 57Fe Mossbauer spectroscopy

In the first known kinetic application of the technique, synchrotron 57Fe-Mössbauer spectroscopy was used to follow the rate of heterogeneous electron transfer between aqueous reagents and a solid phase containing Fe. The solid, a synthetic 57Fe-enriched Fe (III)-bearing pyroaurite-like phase having terephthalate (TA) in the interlayer [Mg3Fe (OH)8(TA)0.5 • 2H2O], was reduced by Na2S2O4 and then reoxidized by K2Cr2O7 by means of a novel flow-through cell. Synchrotron Mössbauer spectra were collected in the time domain at 30-s intervals. Integration of the intensity obtained during a selected time interval in the spectra allowed sensitive determination of Fe(II) content as a function of reaction time. Analysis of reaction end member specimens by both the synchrotron technique and conventional Mössbauer spectroscopy yielded comparable values for Mössbauer parameters such as center shift and Fe (II)/Fe (III) area ratios. Slight differences in quadrupole splitting values were observed, however. A reactive diffusion model was developed that fit the experimental Fe(II) kinetic data well and allowed the extraction of second-order rate constants for each reaction. Thus, in addition to rapidly collecting high quality Mössbauer data, the synchrotron technique seems well suited for aqueous rate experiments as a result of the penetrating power of 14.4 keV X-rays and high sensitivity to Fe valence state

Nuclear forward scattering in particulate matter: dependence of lineshape on particle size distribution

In synchrotron Moessbauer spectroscopy, the nuclear exciton polariton manifests itself in the lineshape of the spectra of nuclear forward scattering (NFS) Fourier-transformed from time domain to frequency domain. This lineshape is generally described by the convolution of two intensity factors. One of them is Lorentzian related to free decay. We derived the expressions for the second factor related to Frenkel exciton polariton effects at propagation of synchrotron radiation in Moessbauer media. Parameters of this Frenkelian shape depend on the spatial configuration of Moessbauer media. In a layer of uniform thickness, this factor is found to be a simple hypergeometric function. Next, we consider the particles spread over a 2D surface or diluted in non-Moessbauer media to exclude an overlap of ray shadows by different particles. Deconvolving the purely polaritonic component of linewidths is suggested as a simple procedure sharpening the experimental NFS spectra in frequency domain. The lineshapes in these sharpened spectra are theoretically expressed via the parameters of the particle size distributions (PSD). Then, these parameters are determined through least-squares fitting of the line shapes.Comment: 13 pages, 12 figure