High-pressure Mössbauer spectroscopy with nuclear forward scattering of synchrotron radiation

Abstract

Using a diamond anvil cell, high-pressure ⁵⁷Fe Mössbauer spectroscopy has been performed with the nuclear forward scattering of synchrotron radiation. A pressure-induced magnetic hyperfine interaction at ⁵⁷Fe in SrFeO_{2, 97} has been detected at 44 GPa and 300 K for a first time by a quantum-beat modulation of the decay rate after collective nuclear excitation by the synchrotron pulse. The basic concept and method used to detect nuclear forward scattering with synchrotron radiation are discussed.     

High-pressure Mössbauer studies of magnetism in RFe2 Laves phases and Eu-chalcogenides

A review is given on current high-pressure studies of magnetism employing the new method of nuclear forward scattering of synchrotron radiation as well as the conventional Mössbauer effect. Comparative studies of the magnetic properties of intermetallic RFe₂ Laves phases and Eu(II)-chalcogenides are described. We present as examples the pressure induced changes in YFe₂ and ScFe₂ at pressures up to 100 GPa as well as studies of EuTe in the NaCl-type and the CsCl-type high-pressure phase. Future high-pressure applications of nuclear resonant scattering will be discussed.     

Nuclear resonant scattering and molecular orbital calculations on an iron(II) spin‐crossover complex

Nuclear resonant scattering of synchrotron radiation was applied to investigate the spin‐crossover complex Fe(tpa)(NCS)₂ (tpa=tris(2‐pyridylmethyl)amine). The nuclear forward scattering experiments are compared with conventional Mössbauer experiments, and the nuclear inelastic scattering experiments are compared with the results from a theoretical normal mode analysis based on molecular orbital calculations.     

Dielectric loss measurements on silver halide sheet crystals

Abstract

A series of studies on the partial X-ray diffuse scattering intensities from ternary alloys analysed through synchrotron radiation experiments has been reviewed. An intensity expression for the short-range order diffuse scattering has been developed, which is necessary in understanding the separation method of an observed X-ray diffuse intensity into partial intensities contributed from different origins. Techniques have been described in detail mainly concerning the Cu₂NiZn alloy, which have shown the benefits of the anomalous scattering effect of synchrotron radiation. The negative partial intensity maximum for the Cu-Ni pair found in the Cu-Ni-Zn alloy has been discussed from the viewpoints of crystallography and thermodynamics. In addition, at the end of the paper, local atomic arrangements causing the diffuse scatterings have been discussed.     

Heterodyne detection of synchrotron radiation

A time integral method for the study of resonant nuclear scattering of synchrotron radiation in the forward direction is presented. The method relies on the interference of radiation scattered by nuclei in two samples, one moving with respect to the other. The method, termed heterodyne detection of synchrotron radiation, gives the same information on hyperfine parameters as the well known differential method. The general formalism is developed for the case where the reference is a single line sample and the investigated sample has magnetic or quadrupole splitting. The first experiments are discussed. A comparison of time differential synchrotron radiation spectroscopy, heterodyne detection and Mössbauer spectroscopy is given.     

How to do resonant nuclear experiments with synchrotron radiation

Summary The use of synchrotron radiation to excite low-lying nuclear resonances is a rapidly developing field showing great promise for hyperfine spectroscopy, phonon spectroscopy and kinetic studies, crystallography, and fundamental physics experiments. Recent technical advances in synchrotron sources, optics, and fast detectors have drastically increased signal rates and expanded the range of samples that can be studied. A typical experiment today uses a high-brightness synchrotron source having X-ray pulses well-separated in time, a meV-bandpass monochromator using perfect crystals of silicon or germanium, a sample containing resonant nuclei, and an avalanche photodiode timing detector. Both coherent and incoherent scattering can be observed; the coherent scattering is used for hyperfine spectroscopy and studies of diffraction interference phenomena, and the incoherent-scattering signal promises to be very useful for phonon spectroscopy and other studies of excitations in condensed systems. At this point seven nuclear isotopes have been used to resonantly scatter synchrotron radiation, but the number is rapidly increasing. Paper presented at the ICAME-95, Rimini 10–16 September 1995.     

Polarization effects in resonant nuclear scattering

Polarization phenomena are present in every radiative transition, whether it is of atomic or nuclear origin. Nuclear resonant scattering of synchrotron radiation is an ideal technique for their study because (a) the probing radiation is in a well characterized polarization state, in most cases linear, (b) the scattered radiation can be efficiently analyzed with polarization filters, and (c) synchrotron pulses are very short compared to the lifetime of a nuclear resonance, resulting in a clean signal. In the following article we describe experimental and theoretical studies of the 14.4 keV Mössbauer resonance of ⁵⁷Fe and its transitions with linear and circular polarization. After introducing the required instrumentation a formalism to calculate time dependent polarization phenomena is derived. With the help of different scattering geometries we illustrate various aspects, such as polarization mixing and selective excitation of subsets of the resonance. Perhaps the most fascinating example is the Faraday geometry where the E-vector rotates several 360^ο turns during the lifetime of the resonant scattering. A comparison of this phenomenon with the optical Faraday effect is given. New powerful synchrotron radiation sources will enable researchers to exploit polarization phenomena in nuclear resonant scattering to detect subtle changes in physically and chemically relevant systems.

     

High-pressure Mössbauer spectroscopy using synchrotron radiation and radioactive sources

A high-pressure ⁵⁷Fe Mössbauer study of SrFeO₃ up to 74 GPa has been performed with diamond-anvil-cell (DAC) using synchrotron radiation and a radioactive point source of ⁵⁷Co in Rh. SrFeO₃ is known as a typical cubic perovskite with a high-valence state of Fe⁴⁺ and shows metallic conductivity at 0.1 MPa down to 4.2 K. Applying an external high pressure, SrFeO₃ has not shown any structural transformation up to 74 GPa keeping an Fe⁴⁺ state but the Néel temperature increases up to 300 K at 18 GPa. The external high pressure may induce the ferromagnetism in SrFeO₃ by a decrease of the interatomic distance of Fe or an increase of the d-band width. ⁵⁷Fe Mössbauer measurements under externally applied longitudinal magnetic field using radioactive ⁵⁷Co in Rh source and also nuclear forward scattering measurements with a linearly polarized synchrotron radiation under external magnetic field indicate the existence of the pressure induced ferromagnetism in SrFeO₃. In this work we compare high-pressure Mössbauer spectroscopy using synchrotron and radioactive sources and summarize the advantages and disadvantages of each method.     

High pressure experiments with synchrotron radiation

Using a diamond anvil cell (DAC), high pressure ⁵⁷Fe Mössbauer spectroscopy has been performed with the nuclear forward scattering of synchrotron radiation. We used monochromatized synchrotron radiation from an in‐vacuum type undulator as a high‐density strong Mössbauer source with a quite small beam size. Pressure‐induced magnetic hyperfine interactions at ⁵⁷Fe in SrFeO_2.97 has been detected at 74 GPa by a quantum‐beat modulation of the decay rate after collective nuclear excitation with the synchrotron radiation pulse. Evidence for a transition from antiferromagnetism to ferromagnetism of Fe in SrFeO_2.97 at 74 GPa and 300 K has been obtained from the nuclear forward scattering under a transverse magnetic field.     

A portable ultrahigh‐vacuum system for advanced synchrotron radiation studies of thin films and nanostructures: EuSi2 nano‐islands

A portable ultrahigh‐vacuum system optimized for in situ variable‐temperature X‐ray scattering and spectroscopy experiments at synchrotron radiation beamlines was constructed and brought into operation at the synchrotron radiation facility ANKA of the Karlsruhe Institute of Technology, Germany. Here the main features of the new instrument are described and its capabilities demonstrated. The surface morphology, structure and stoichiometry of EuSi₂ nano‐islands are determined by in situ grazing‐incidence small‐angle X‐ray scattering and X‐ray absorption spectroscopy. A size reduction of about a factor of two of the nano‐islands due to silicide decomposition and Eu desorption is observed after sample annealing at 1270 K for 30 min.     

Introduction to nuclear resonant scattering with synchrotron radiation

The concepts leading to the application of synchrotron radiation to elastic and inelastic nuclear resonant scattering are discussed. The resulting new experimental techniques are compared to conventional Mössbauer spectroscopy. A survey of situations that favor experiments with synchrotron radiation is offered.

     

Phonon Spectroscopy of Oriented hcp Iron

High-pressure phonon spectroscopy was performed on iron in the bcc and hcp phase up to 40 GPa using the nuclear inelastic scattering (NIS) of synchrotron radiation (SR). In hcp iron we observe differences in the density of phonon states for spectra measured with different orientations of the diamond anvil cell (DAC) with respect to the SR beam. These differences are attributed to a preferred orientation of the hexagonal c -axis along the load axis of the DAC. These texture effects are used, in conjunction with theoretical calculations, to extract density of phonon states as seen parallel and perpendicular to the c -axis of hcp iron.     

Resonant two‐magnon Raman scattering in high‐Tc cuprates

Resonance enhancement of one‐phonon, two‐phonon, and two‐magnon Raman scattering in a general, exactly solvable, multiband model is explained in a way that is in accordance with the general analytical properties of the total optical conductivity tensor. Using this approach, the charge‐transfer limit of the Emery three‐band model is examined to explain resonance enhancement of the two‐magnon Raman spectra of high‐T_c cuprates, which is found in experiments to be of 3 orders of magnitude. While previous Raman and optical conductivity analyzes of the cuprates, based on the single‐band Hubbard model, are found to be consistent with the picture where one hole per one CuO₂ unit is localized on the Cu ion, the present three‐band approach allows the study of the opposite, strong copper‐oxygen hybridization limit, which is found to be in agreement with the results of nuclear magnetic resonance (NMR) and one‐phonon Raman scattering experiments. Copyright © 2010 John Wiley & Sons, Ltd.     

Dependence of nuclear diffraction on the azimuthal angle: (002)- and (0010)-reflections of YIG

Nuclear diffraction of synchrotron radiation has been investigated using YIG single crystals in different scattering geometries. Time resolved quantum beat spectra of pure nuclear (002) and (0010) Bragg reflections were observed in a set-up where the hyperfine interaction was kept constant, while the azimuthal angle in the (001) surface between the [100] axis and the scattering plane (k _in,k _out) was varied. The time spectra were analyzed by means of the dynamical theory for coherent nuclear scattering. The results revealed the high sensitivity of this experimental technique on the complete set of hyperfine interaction parameters and on the specific geometrical conditions for nuclear diffraction of polarized γ-rays.     

Pressure-induced valence transition in EuNi2Ge2 studied by 151Eu nuclear forward scattering of synchrotron radiation

Hyperfine Interactions - We present the first application of nuclear forward scattering (NFS) of synchrotron radiation by the 21.5 keV transition of 151Eu for a high-pressure study. After...     

Relaxation experiments with synchrotron radiation

Relaxation phenomena show up in standard energy domain Mössbauer spectra via line broadening. The evaluation of such spectra is in most cases done by adopting the stochastic theory mainly developed in the 60s and 70s. Due to the time structure and the polarization of the synchrotron radiation nuclear resonance forward scattering in the time domain gives valuable information on relaxation mechanisms. We report here mainly on Nuclear Forward Scattering (NFS) experiments investigating the paramagnetic relaxation of the Fe³⁺ ion in (NH)₄Al_0.95 ⁵⁷Fe_0.05(SO₄)₂·12H₂O and briefly on recent investigations on charge fluctuations in Eu₃S₄.     

Enhancement and speedup in nuclear resonant diffraction

The interaction of Mössbauer radiation with the nuclei in a single crystal provides the unique possibility to enhance the coherent channel in nuclear resonance scattering by means of a properly phased excitation of the scattering centers. When a primary beam is incident in the exact Bragg direction, all nuclei are excited in phase. The resonance parameters of such a collective nuclear excitation of a perfect single crystal (γ-exciton) are entirely different from those of an individual nuclear excitation. In Bragg geometry diffraction, the resonance lines are shifted and broadened (enhancement effect), the lifetime of the collective excited state is shortened (speedup effect) and the reflectivity becomes total (suppression effect). Recent experiments arc reviewed, where these effects were studied in the resonant diffraction of Mössbauer and of synchrotron radiation.

     

Phonon density of states in epitaxial FE/CR(0 0 1) superlattices

Incoherent nuclear resonant absorption of synchrotron radiation at the 14.413 keV nuclear resonance of ⁵⁷Fe was employed to measure directly the Fe-projected (partial) phonon density of states (DOS) in epitaxial FeCr(0 0 1) superlattices and in an ⁵⁷Fe_0.03Cr_0.97(0 0 1) alloy film MBE-grown on MgO(0 0 1). The measurements were performed at 300 K with 2.3 meV energy resolution around 14.413 keV. At the interfaces, longitudinal vibrations of Fe atoms are suppressed, and a strong resonance phonon mode appears near 23 meV. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synchrotron Mössbauer reflectometry using stroboscopic detection

The concept of the heterodyne/stroboscopic detection of nuclear resonance scattering of synchrotron radiation is extended to the grazing incidence geometry. Model calculations for an antiferromagnetic [⁵⁷Fe/Cr]₂₀ multilayer are shown and discussed. Principles and methodological aspects of stroboscopic synchrotron Mössbauer reflectometry are briefly reviewed.     

Recent progress on neutron studies of YBa2Cu3O6+x

A review is given of recent developments in inelastic neutron scattering experiments on the high temperature superconductor YBa_2Cu_3O_7 and its antiferromagnetic precursor YBa_2Cu_3O_6.2. These include the detection of high energy “optical” spin waves and the determination of the full spin Hamiltonian in YBa_2Cu_3O_6.2, a detailed study of the 40 meV magnetic resonance peak in the superconducting state of YBa_2Cu_3O_7, and experiments on the effect of superconductivity on phonon lifetimes in YBa_2Cu_3O_7. This revised version was published online in August 2006 with corrections to the Cover Date.