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.     

Synchrotron Mössbauer source of57Fe radiation

A nonradioactive source of Mössbauer radiation is described for use in Mössbauer absorption and scattering spectroscopy. The radiation is generated by synchrotron Xrays in an iron borate single crystal set in diffraction conditions at the Néel temperature (75.3°C). Like a conventional Mössbauer source the new Synchrotron Mössbauer (SM) source emits singleline radiation of about natural linewidth, but in addition the emitted radiation is fully recoilless, highly directed and of pure linear polarization. An extremely high suppression of the electronic scattering is achieved. The latter circumstance allows one to perform Mössbauer experiments using pulsed synchrotron radiation in a steady state mode as in a normal Mössbauer measurement.The theory of the SM source is developed. First Mössbauer spectra obtained with the SM source are shown. Applications of the SM source are discussed.     

Backscattering Mössbauer MIMOS II and XRF studies on tektites from different strewn fields

Room temperature ⁵⁷Fe Mössbauer spectroscopy has been used to obtain information on the redox and coordination of iron in tektites. A MIMOS II spectrometer in backscattering geometry has been used in the study, so that no sample preparation at all was required. X-ray fluorescence has been used to determine the composition of the tektites. Mössbauer spectra have been deconvoluted using three extended Voigt-based profiles to allow quantitative analysis of iron atoms valence and coordination. In all tektites, the Fe $^{2+ }$ sites have been distinguished in Fe with octahedral and tetrahedral coordination. The Fe $^{2+}$ octahedral sites show a region of isomer shift (IS) and quadrupole splitting (QS), IS $=$ 1.02–1.14 mm/s and QS $=$ 1.82–2.12 mm/s, relative to $\alpha $ -Fe. The Fe $^{2+ }$ tetrahedral sites show a region of hyperfine parameters of IS = 0.59–0.89 mm/s and QS = 1.14–1.60 mm/s. The Fe³⁺sites show IS = 0.11–0.33 mm/s and QS = 0.02–0.04 mm/s. The Fe³⁺/Fe²⁺ ratio was found to be 0.025–0.149.     

Recent theoretical and experimental development of Mössbauer effect with synchrotron radiation

The elements of a dedicated beam line are introduced. Computer simulations of the nuclear monochromator response to an incident broad band of radiation show the special features of the new source-speed up, dynamical beats, quantum beats and polarization mixing. Experiments with YIG and FeBO₃ confirm the theoritical picture. It is shown that time differential measurements have the potential of greatly improving the accuracy of future experiments. New fields of investigations will be broadband spectroscopy in the eV range and -optics.Dedicated to Ulrich Bonse on the occasion of his 60th birthday     

Fast detectors for Mössbauer spectroscopy

The methods to increase the productivity (statistical quality) of Mössbauer measurements have been considered. Some fast detectors for gamma- and secondary radiation have been described. These detectors allow in many cases to essentially reduce the time for the Mössbauer spectra accumulation with a given productivity.     

Modulation of Mössbauer radiation by pulsed laser excitation

Experimental results on the observation of the modulation of Mössbauer radiation by pulsed laser radiation are presented. The time domain spectra agree well with the model of the frequency modulation of the Mössbauer radiation during the passage of the radiation through a vibrating resonance medium. The proposed methodology may be used for the study of opto-acoustic phenomena.     

Study of tin amalgam mirrors by 119Sn Mössbauer spectroscopy and other analytical methods

From the beginning of the 16 ^th until the end of the 19 ^th century the most widely used mirrors consisted of a pane of glass backed with a reflecting layer of tin-mercury amalgam. They were made by sliding the glass pane over a tin foil covered with liquid mercury. After removal of the superfluous mercury, tin amalgam formed slowly at ambient temperature and yielded a reflecting layer adhering to the surface of the glass. Such mirrors often deteriorate in the course of time by oxidation of the tin in the amalgam to stannous or stannic oxide. ¹¹⁹Sn Mössbauer spectroscopy, scanning electron microscopy, micro-XRF and X-ray diffraction have been used to study this deterioration process. The studied specimens were a modern mirror made for the reconstruction of the Green Vault in Dresden in the early 2000s, two rather well preserved German mirrors from the 17 ^th and 19 ^th centuries and several strongly deteriorated specimens of Baroque mirrors from the south of Spain. The modern mirror consists mainly of a Sn_0.9Hg_0.1 amalgam with only 2 % of SnO₂. The older German mirrors showed more pronounced oxidation, containing 12 and 15 % of SnO₂, which did not noticeably impair their reflectivity. In the samples from the Spanish mirrors at best a few percent of metallic phase was left. The majority of the tin had oxidised to SnO₂, but between 8 and 20 % of the tin was present as SnO. X-ray diffraction yielded similar results and micro-XRF mapping using synchrotron radiation for excitation gave information on the distribution of Sn and Hg in the reflecting layer of the mirrors.     

Implementation of a preamplifier-amplifier system for radiation detectors used in Mössbauer spectroscopy

We report the assembly and testing of a preamplification and amplification system for pulses produced by gaseous radiation detectors commonly used in Mössbauer spectroscopy. The system is composed by a pair of commercial integrated circuits A203 and A206, which operate as charge sensitive preamplifier-shaping amplifier and linear amplifier-low level discriminator, respectively. The integrated circuits were interconnected in the unipolar output mode and placed inside a metallic shielding, which prevents noise amplification for a suitable signal-noise ratio. The system was tested by irradiating a proportional counter LND-45431 with characteristic X rays of 6.3 keV and gamma rays of 14.4 keV emitted by a Mössbauer radioactive source of ⁵⁷Co (Rh). Unipolar pulses with Gaussian profile were obtained at the output of the linear amplifier, whose amplitudes were close to 0.4 V for 6.3 keV X rays and 1.4 V for 14.4 keV gamma rays. Pulse height spectra showed that the system allows a satisfactory identification of the X-rays and gamma rays emitted by the ⁵⁷Co source, giving the possibility to make a good selection of the 14.4 keV peak for having a suitable signal-noise ratio in the Mössbauer spectra. Absorption percentages of 14 % were found by taking the Mössbauer spectra of a natural iron absorber. The assembly and tests of the system are presented through this paper.     

The Mössbauer effect and magnetism

The Mössbauer effect enabled the magnetic hyperfine splitting (hfs) in ferromagnetic solids to be observed directly for the first time. It was quickly extended to measurements on antiferromagnets, ferrimagnets and paramagnets, and is now well established as a probe for the study of magnetic materials. Applications have ranged from the old problem of the state of the iron atoms in ferromagnetic alloys to the new magnetic materials, e.g. amorphous magnets, spin glasses, fine particle magnets and multilayers. Some examples where the Mössbauer effect has made an important contribution are described.     

Zero-point Oscillations and Mössbauer Effect

The peculiar properties of the Mössbauer effect provide an important test, and possibly a challenge, to Quantum Physics. The zero-point momentum reservoir of the mechanical oscillators forming a crystal lattice is indicated, in the present paper, as the possible way out from apparent contradictions of the observed features with both momentum conservation and the uncertainty principle.     

Radiation-induced sidebands in a Mössbauer spectrum using synchrotron radiation

The resonant interactions of SR with nuclei have been studied in the magnetic dipole approximation. The spontaneous emission spectrum of the nuclei interacting with the SR consists of three types of photons with energiesE-2, E, E + 2, whereE is the energy corresponding to the unperturbed nuclear transition. The relative intensities of the transitions are in the ratios 121. A conventional ME spectrum, the source being an ensemble of SR excited nuclei and a single-line absorber, will display three resonances; the two outer ones are SR-induced sidebands having equal intensity and width.     

Synchrotron radiation based Mössbauer absorption spectroscopy of various nuclides

Synchrotron-radiation (SR) based Mössbauer absorption spectroscopy of various nuclides is reviewed. The details of the measuring system and analysis method are described. Especially, the following two advantages of the current system are described: the detection of internal conversion electrons and the close distance between the energy standard scatterer and the detector. Both of these advantages yield the enhancement of the counting rate and reduction of the measuring time. Furthermore, SR-based Mössbauer absorption spectroscopy of ⁴⁰K, ¹⁵¹Eu, and ¹⁷⁴Yb is introduced to show the wide applicability of this method. In addition to these three nuclides, SR-based Mössbauer absorption spectroscopy of ⁶¹Ni, ⁷³Ge, ¹¹⁹Sn, ¹²⁵Te, ¹²⁷I, ¹⁴⁹Sm, and ¹⁸⁹Os has been performed. We continue to develop the method to increase available nuclides and to increase its ease of use. The complementary relation between the time-domain method using SR, such as nuclear forward scattering and the energy-domain methods such as SR-based Mössbauer absorption spectroscopy is also noted.     

Proposal for a test of the relativity principle by using Mössbauer synchrotron radiation

The present paper represents the simplest proof that the general relativity principle does not come to the particular relativity principle in case of inertial motion in an empty space. It admits an existence of phenomena, where a violation of the particular relativity principle occurs within the scope of the general relativity principle. Under modern development of experimental techniques, a search of such hypothetical phenomena can be made only by means of the Mössbauer effect. A scheme of possible experiment has been proposed.     

Mössbauer optics of synchrotron radiation at an isotopic boundary

The inelastic coherent Mössbauer scattering (ICMS) of synchrotron radiation at an isotopic boundary—a flat interface between two regions of matter which have different concentrations of the Mö ssbauer isotope—is investigated theoretically. Attention is focused primarily on the ICMS component for which the absorption of a synchrotron radiation photon by a nucleus occurs with recoil, i.e., with the creation or annihilation of lattice phonons, and the subsequent process of reemission of a photon by the Mössbauer nucleus occurs without recoil, as a result of which radiation is pumped from the wide synchrotron radiation line into the narrow Mö ssbauer line. Formulas similar to the Fresnel formulas, well known in optics, for the transmission and reflection of light at a dielectric boundary are obtained for ICMS at an isotopic boundary. Specifically, it is shown that the angle of reflection for ICMS at an isotopic boundary is different from the angle of mirror reflection of a synchrotron radiation beam, and the direction of the ICMS transmitted through the isotopic boundary depends on the deviation of its frequency from the exact value of the Mössbauer resonance frequency and in general is different from the direction of propagation of the synchrotron radiation beam. The suppression of ICMS at grazing angles of incidence of the synchrotron radiation beam is analyzed. A similar problem is solved for a plate-shaped sample containing a Mössbauer isotope. It is shown that the specific nature of the ICMS at an isotopic boundary could be helpful in the problem of Mö ssbauer filtering of synchrotron radiation.     

Mössbauer spectroscopy for optimising systems for environmental remediation

Mössbauer spectroscopy was used to examine Fe-containing microporous materials zeolite X and AlPO-5 designed for the reduction of Cr(VI) to Cr(III) and Cr(III) uptake. XRD, XRF, EPR and XPS were used to provide supporting information. AlPO-5 was found to only incorporate inactive Fe(III), whilst Fe(II) and Fe(III) were identified in zeolite X across a distribution of sites. Fe coordinates to oxygen atoms belonging to both water molecules and framework positions. EPR confirmed these findings and showed how the site distribution narrows upon dehydration. XPS showed that a distribution of Fe sites exists at the sample surface. Mössbauer spectroscopy was also used to track oxidation and reduction processes in Fe-zeolite X. Over time, gradual Fe oxidation takes place in air-exposed samples. Reduction under hydrogen flow increases the populations of low oxidation state Fe; as the reaction time increases, Fe(II) populations first increase, then decrease as Fe(0) is evolved.     

Mössbauer and magnetic characterization of TbRhSn

The intermetallic compound TbRhSn was investigated in detail by X-ray, magnetic susceptibility measurements and ¹¹⁹Sn Mössbauer spectroscopy. This compound undergoes a transition from a paramagnetic to an antiferromagnetic state at T _N = 20.8(2) K. The ¹¹⁹Sn Mössbauer spectrum recorded at 4.2 K can be well fitted as a composition of three subspectra with the same intensities, magnitudes of H _hf, ΔE _Q, and δ _is, in agreement with the model of triangular-like antiferromagnetic arrangements of equal magnetic Tb moments lying in the basal ab-plane deduced from neutron diffraction studies (Szytu?a et al., J Alloys Compd 244:94–98, 1996).     

Mössbauer studies of baotite and bafertisite

The Mössbauer effect was used to study silicate minerals of baotite and bafertisite at 298 K and 95 K. Each spectrum of baotite at 298 K and 95 K consists of two doublets, and they are contributed from Fe²⁺ and Fe³⁺ in the octahedral Tisites, respectively. Each spectrum of bafertisite at 298 K and 95 K is composed of two doublets, and they are mainly caused by Fe²⁺ in the octahedral Fe(I) and Fe(II)sites, respectively. The average effective ionic radii of the Ti sites in baotite and the Fe(I) and Fe(II)sites in bafertisite were estimated based on the correlation of the isomer shifts with the average effective ionic radii in silicates, and they are 0.56 , 0.73 and 0.73 , respectively.     

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.