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

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

Six-reflection meV-monochromator for synchrotron radiation

A design is presented for a cryogenically stabilized monochromator for 10–40 keV synchrotron radiation that uses six crystal reflections to achieve a meV-bandpass with high efficiency

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

Synchrotron Mössbauer spectroscopy using high-speed shutters

A new method of performing Mössbauer spectroscopy using a fast shutter in combination with microfocused synchrotron radiation is demonstrated

Dynamics of iron atoms across the pressure-induced Invar transition in Pd_3Fe

The ^(57)Fe phonon partial density of states (PDOS) in L1_2-ordered Pd_3Fe was studied at high pressures by nuclear resonant inelastic x-ray scattering (NRIXS) measurements and density functional theory (DFT) calculations. The NRIXS spectra showed that the stiffening of the ^(57)Fe PDOS with decreasing volume was slower from 12 to 24 GPa owing to the pressure-induced Invar transition in Pd_3Fe, with a change from a high-moment ferromagnetic (FM) state to a low-moment (LM) state observed by nuclear forward scattering. Force constants obtained from fitting to a Born–von Kármán model showed a relative softening of the first-nearest-neighbor (1NN) Fe-Pd longitudinal force constants at the magnetic transition. For the FM low-pressure state, the DFT calculations gave a PDOS and 1NN longitudinal force constants in good agreement with experiment, but discrepancies for the high-pressure LM state suggest the presence of short-range magnetic order

High-energy resolution, high-angular acceptance crystal monochromator

The design principles, construction and characterization of a 4- bounce dispersive crystal monochromator is discussed. This monochromator is designed to reduce the bandpass of synchrotron radiation to 10--50 meV level, without sacrificing angular acceptance. This is achieved by combining an asymmetrically-cut, low order reflection with a symmetrically-cut, high order reflection in a nested configuration. This monochromator is being used as a beam conditioner for nuclear resonant scattering of synchrotron radiation to produce x-rays with {mu}eV{minus}neV resolution in the hard x-ray regime