The 57Fe Synchrotron Mössbauer Source at the ESRF

The design of a ⁵⁷Fe Synchrotron Mössbauer Source (SMS) for energy‐domain Mössbauer spectroscopy using synchrotron radiation at the Nuclear Resonance beamline (ID18) at the European Synchrotron Radiation Facility is described. The SMS is based on a nuclear resonant monochromator employing pure nuclear reflections of an iron borate (⁵⁷FeBO₃) crystal. The source provides ⁵⁷Fe resonant radiation at 14.4 keV within a bandwidth of 15 neV which is tunable in energy over a range of about ±0.6 µeV. In contrast to radioactive sources, the beam of γ‐radiation emitted by the SMS is almost fully resonant and fully polarized, has high brilliance and can be focused to a 10 µm × 5 µm spot size. Applications include, among others, the study of very small samples under extreme conditions, for example at ultrahigh pressure or combined high pressure and high temperature, and thin films under ultrahigh vacuum. The small cross section of the beam and its high intensity allow for rapid collection of Mössbauer data. For example, the measuring time of a spectrum for a sample in a diamond anvil cell at ～100 GPa is around 10 min, whereas such an experiment with a radioactive point source would take more than one week and the data quality would be considerably less. The SMS is optimized for highest intensity and best energy resolution, which is achieved by collimation of the incident synchrotron radiation beam and thus illumination of the high‐quality iron borate crystal within a narrow angular range around an optimal position of the rocking curve. The SMS is permanently located in an optics hutch and is operational immediately after moving it into the incident beam. The SMS is an in‐line monochromator, i.e. the beam emitted by the SMS is directed almost exactly along the incident synchrotron radiation beam. Thus, the SMS can be easily utilized with all existing sample environments in the experimental hutches of the beamline. Owing to a very strong suppression of electronic scattering for pure nuclear reflections (～10^?9), SMS operation does not required any gating of the prompt electronic scattering. Thus, the SMS can be utilized in any mode of storage ring operation.     

Nuclear resonance reflectivity from a [57Fe/Cr]30 multilayer with the Synchrotron Mössbauer Source

Mössbauer reflectivity spectra and nuclear resonance reflectivity (NRR) curves have been measured using the Synchrotron Mössbauer Source (SMS) for a [⁵⁷Fe/Cr]₃₀ periodic multilayer, characterized by the antiferromagnetic interlayer coupling between adjacent ⁵⁷Fe layers. Specific features of the Mössbauer reflectivity spectra measured with π‐polarized radiation of the SMS near the critical angle and at the `magnetic' maximum on the NRR curve are analyzed. The variation of the ratio of lines in the Mössbauer reflectivity spectra and the change of the intensity of the `magnetic' maximum under an applied external field has been used to reveal the transformation of the magnetic alignment in the investigated multilayer.     

Lancaster delftware: a Raman spectroscopy,electron microscopy and Mössbauer spectroscopy compositional study

In 2008, excavations were conducted by the Northern Ceramic Society at the site of the former Lancaster delftware potworks, which operated between 1754 and about 1790. The recovered sherds have been non‐destructively examined by Raman and electron microscopies and the iron phases in the biscuit by Mössbauer spectroscopy. These methods have provided a new understanding of the mineralogy of the delftware produced at Lancaster using clay imported from Carrickfergus in Ireland and blended with the local ferruginous‐aluminous clays. This has implications for the attribution of delftware produced at Liverpool, Bristol, Scotland and Ireland. The Carrickfergus clay has been found to be highly dolomitic resulting in the body of the delftware forming diopside and the magnesian olivine forsterite, when fired. Brookite had not converted to rutile, nor had tridymite, nor cristobalite formed; the K‐feldspars did not undergo further chemical reactions, and the observation of metakaolin would suggest that the biscuit firing temperature was in the order of 800–900 °C. Chalcedony containing moganite was established as the silica source. A cobalt‐containing lead‐tin glaze was applied to the biscuit body and, after decorating, was fired. The mineralogy of the pigments used to decorate the objects indicate the yellow to be the PbSbSn triple oxide, the green to be a copper silicate mixed with lead‐tin yellow, the purple and browns to be manganese silicates and the blue to contain cobalt spinels and cobalt pyroxenes. Diopside crystals together with recrystallised tin agglomerates have been observed floating within the glaze. Copyright © 2015 John Wiley & Sons, Ltd.     

Raman spectroscopy of Limehouse porcelain sherds supported by Mössbauer spectroscopy and scanning electron microscopy

The Limehouse pot works, founded probably in the early 1745, was one of the earliest porcelain works established in England. It closed in June 1748. The factory site at 20 Fore Street Limehouse, London, was excavated by the Museum of London, Department of Greater London Archaeology in 1990, recovering 1402 sherds. A number of these sherds has now been examined by Raman spectroscopy, scanning electron microscopy and one by Mössbauer spectroscopy. Different porcellaneous formulations have been identified; namely, an experimental Si–Al body with a Si–Al–Ca glaze and a Si–Al–Ca body containing minor Pb and Mg and covered with a Si–Pb–Ca glaze. Several sherds were intermediate between these compositions. Most sherds failed to reach vitrification temperature and lack translucency. Mössbauer spectroscopy indicated that one sherd had been fired under mildly reducing conditions. These results have enabled conclusions to be reached in respect of the raw materials, body and glaze compositions and firing and glazing conditions used at Limehouse. Copyright © 2013 John Wiley & Sons, Ltd.     

Mössbauer spectroscopy evidence of intrinsic non‐stoichiometry in iron telluride single crystals

The FeTe parent compound for iron‐superconductor chalcogenides was studied applying Mössbauer spectroscopy accompanied by ab initio calculations of electric field gradients at the iron nuclei. Room‐temperature (RT) Mössbauer spectra of single crystals have shown asymmetric doublet structure commonly ascribed to contributions of over‐stoichiometric iron or impurity phases. Low‐temperature Mössbauer spectra of the magnetically ordered compound could be well described by four hyperfine‐split sextets, although no other foreign phases different from Fe_1.05Te were detected by XRD and microanalysis within the sensitivity limits of the equipment. Density functional ab initio calculations have shown that over‐stoichiometric iron atoms significantly affect electron charge and spin density up to the second coordination sphere of the iron sub‐lattice, and, as a result, four non‐equivalent groups of iron atoms are formed by their local environment. The resulting four‐group model consistently describes the angular dependence of the single crystals Mössbauer spectra as well as intensity asymmetry of the doublet absorption lines in powdered samples at RT. We suppose that our approach could be extended to the entire class of FeSeTe_x compounds, which contain excess iron atoms.

     

Development of an energy‐domain 57Fe‐Mössbauer spectrometer using synchrotron radiation and its application to ultrahigh‐pressure studies with a diamond anvil cell

An energy‐domain ⁵⁷Fe‐Mössbauer spectrometer using synchrotron radiation (SR) with a diamond anvil cell (DAC) has been developed for ultrahigh‐pressure measurements. The main optical system consists of a single‐line pure nuclear Bragg reflection from an oscillating ⁵⁷FeBO₃ single crystal near the Néel temperature and an X‐ray focusing device. The developed spectrometer can filter the Doppler‐shifted single‐line ⁵⁷Fe‐Mössbauer radiation with a narrow bandwidth of neV order from a broadband SR source. The focused incident X‐rays make it easy to measure a small specimen in the DAC. The present paper introduces the design and performance of the SR ⁵⁷Fe‐Mössbauer spectrometer and its demonstrative applications including the newly discovered result of a pressure‐induced magnetic phase transition of polycrystalline ⁵⁷Fe₃BO₆ and an unknown high‐pressure phase of Gd⁵⁷Fe₂ alloy placed in a DAC under high pressures up to 302 GPa. The achievement of Mössbauer spectroscopy in the multimegabar range is of particular interest to researchers studying the nature of the Earth's core.     

Grazing‐incidence synchrotron‐radiation 57Fe‐Mössbauer spectroscopy using a nuclear Bragg monochromator and its application to the study of magnetic thin films

Energy‐domain grazing‐incidence ⁵⁷Fe‐Mössbauer spectroscopy (E‐GIMS) with synchrotron radiation (SR) has been developed to study surface and interface structures of thin films. Highly brilliant ⁵⁷Fe‐Mössbauer radiation, filtered from SR by a ⁵⁷FeBO₃ single‐crystal nuclear Bragg monochromator, allows conventional Mössbauer spectroscopy to be performed for dilute ⁵⁷Fe in a mirror‐like film in any bunch‐mode operation of SR. A theoretical and experimental study of the specular reflections from isotope‐enriched (⁵⁷Fe: 95%) and natural‐abundance (⁵⁷Fe: ～2%) iron thin films has been carried out to clarify the basic features of the coherent interference between electronic and nuclear resonant scattering of ⁵⁷Fe‐Mössbauer radiation in thin films. Moreover, a new surface‐ and interface‐sensitive method has been developed by the combination of SR‐based E‐GIMS and the ⁵⁷Fe‐probe layer technique, which enables us to probe interfacial complex magnetic structures in thin films with atomic‐scale depth resolution.     

The role of Sb in the structure of Sb2O3–B2O3 binary glasses—an NMR and Mössbauer spectroscopy study

Glasses of general formula xSb₂O₃ (1−x)B₂O₃ (0x0.8) have been prepared by conventional melt- quenching. Mössbauer spectroscopy shows that a fraction of the Sb³⁺ is converted to Sb⁵⁺ and this fraction increases with x. High-field ¹¹B MAS NMR gives well-resolved resonances from boron atoms which are 3- and 4-coordinated to oxygen. The fraction of 4-coordinated boron, N₄, goes through a maximum value of 0.12±0.01 at x=0.5. The position of the maximum in N₄ is consistent with the cation potential for Sb³⁺, as observed for other systems. However, the low value of N₄ at this maximum is not so readily explained. The values are similar to those predicted if [BO₄]⁻ were stabilised by [SbO₄]⁺ but the trends with composition are different.     

Topology induced anomalous plasmon modes in metallic Möbius nanorings

We report on the theoretical investigation of plasmonic resonances in metallic Möbius nanorings. Half‐integer numbers of resonant modes are observed due to the presence of an extra phase π provided by the topology of the Möbius nanostrip. Anomalous plasmon modes located at the non‐orientable surface of the Möbius nanoring break the symmetry that exist in conventional ring cavities, thus enable far‐field excitation and emission as bright modes. The far‐field resonant wavelength as well as the feature of half‐integer mode numbers is constant to the change of charge distribution on the Möbius nanoring due to the topology of Möbius ring. Owing to the ultra‐small mode volume induced by the remaining dark feature, an extremely high sensitivity as well as a remarkable figure of merit is obtained in our numerical calculations for sensing performance. The topological metallic nanostructure provides a novel platform for the investigation of localized surface plasmon modes exhibiting unique phenomena for potential plasmonic applications.

     

Mechanisms and Möbius strips: understanding dynamic processes in annulenes

Exploratory computational studies on annulenes with planar, Möbius, and two‐twist topologies have resulted in new mechanisms to explain facile thermal configuration change (cis‐trans isomerization) for medium‐sized annulenes ([12]‐ to [16]annulene). Möbius π‐bond shifting through both aromatic and antiaromatic transition states, two‐twist π‐bond shifting, and planar nondegenerate π‐bond shifting can all be invoked to explain experimental results. Moreover, a simple bond‐shift rule, which is based on the change in number of trans C?C double bonds (Δtrans), was developed that predicts the topology of the transition state(s) necessary to effect the desired cis‐trans isomerization. The bond‐shift rule was also applied to configuration change in dehydro[12]annulene. Finally, extensive investigation of the [14]annulene hypersurface revealed that numerous Möbius minima exist within 10 kcal/mol of the global minimum. Copyright © 2012 John Wiley & Sons, Ltd.     

Mössbauer analysis on the magnetic properties of Fe–Co nanoparticles synthesized by chemical vapor condensation process

The magnetic properties of Fe–Co nanoparticles synthesized by chemical vapor condensation (CVC) process were investigated. Effect of CVC processing variables on the magnetic properties was analyzed in detail, using Mössbauer spectroscopy, XRD, BET and HRTEM. The synthesized particles were nearly spherical, and their surfaces were identified to be -FeOOH, γ-FeOOH and Fe₃O₄, but not -Fe₂O₃. The magnetic properties were strongly influenced by CVC processing parameters. The increase of cobalt content had changed the magnetic property of the sample. However, when the decomposition temperature and the oxygen content in the carrier gas (Ar) were increased, the magnetic property reduced with decreasing the average particle size. Increasing the vacuum pressure in the chamber resulted in that the magnetic field reinforced with the increase of average particle size.     

Response to “The Mössbauer rotor experiment and the general theory of relativity” by C. Corda

We show that a new attempt by Corda (2016), just like his previous attempt (Corda, 2015) that we had answered before (A.L. Kholmetskii et al., 2015), to reinterpret Mössbauer experiments in a rotating system as a “new, strong and independent proof of the correctness of Einstein’s vision of gravity” is erroneous. In addition, we demonstrate that Corda’s criticism of Yarman–Arik–Kholmetskii gravitation theory (in short YARK), is based on the application of ill-posed logic; thus rendering his claims against YARK as unfounded.     

基于同时的相对性对钟慢尺缩效应的再认识

同时的相对性、钟慢效应和尺缩效应是狭义相对论时空观的主要内容.鉴于同时性是时空测量的基础,本文从同时的相对性出发详述了对钟慢效应和尺缩效应的再认识:钟慢效应是运动时钟走时率变慢和校表问题的综合表现,其实质是同时的相对性在时间量度上的直接反映;尺缩效应的实质是同时的相对性在空间量度上的反映,也是不同观测者对同一客观事实的不同时空描述.     

M6ssbauer studies on the shape effect of Fes4.94Si9.6sA15.38 particles on their microwave permeability4

Ball milling for long time （such as 10, 20, and 30 h） can transform Fe84.94Si9,68A15.38 alloy powders with irregular shapes into flakes. X-ray diffraction （XRD） and M6ssbauer measurements have proven that the unmilled particles and the flakes obtained by milling for 10 h have the same D03-type superlattice structure. The flakes obtained by milling for 20 h and 30 h have the same disorder a-Fe（Si, A1） structure. There are more than 6 absorption peaks in the transmis- sion MSssbauer spectra （TMSs） for the particles with D03-type superlattice structure, which can be fitted with 5 sextets representing 5 different Fe-site environments. However, only 6 TMS absorption peaks have been found for particles with a disorder a-Fe（Si, A1） structure, which can be fitted with the distributions of M6ssbauer parameters （Bhf, isomer shift）. The TMS results show that the flaky particles have a stronger tendency to possess the planar magnetic anisotropy. As the result, the flakes have larger microwave permeability values than particles with irregular shapes. The conversion electron M6ssbauer spectra （CEMSs） also show the significantly different Fe-sites environments between the alloy surface and the inside.     

Superconductivity in non-stoichiometric and tin-substituted La2CuO4: preparation, characterization, Mössbauer and microwave-absorption studies

Two samples of non-stoichiometric La₂CuO₄ were synthesized, one with La/Cu<2, and the other with 10% Sn substituting Cu. They were investigated by X-ray diffraction, Mössbauer spectroscopy, and microwave-absorption techniques. The microwave-absorption data indicated that they were both superconducting, with the transition temperatures T_c of 40.5 and 41.5 K, the one doped with Sn possessing the higher T_c. The Mössbauer spectra revealed that there exist two kinds of Sn(IV) atoms disordered with Cu. Their isomer shift, δ=−0.244(4) mm/s, is in agreement with Sn(IV) coordinated by oxygen. One site was characterized by a single Mössbauer line, being associated with a weakly distorted environment, wherein the Sn, coordinated more symmetrically, is surrounded by four Cu²⁺ ions. On the other hand, the other site, characterized by a Mössbauer doublet exhibited a quadrupole splitting Δ=1.07(2) mm/s, being associated with a highly distorted coordination, explained to be due to Sn occupying two adjacent cationic sites. To our knowledge, such a substitution for copper ions not resulting in a decrease of T_c has not been reported previously.     

Study of the magnetism and the magnetic anisotropy of Fe layers in Ni/Fe/Ni(1 1 1) by Mössbauer spectroscopy

The hyperfine field and the magnetic anisotropy of a Fe layer as a function of thickness have been investigated in several Ni/⁵⁷Fe_x/Ni(1 1 1) trilayers with relatively thick Ni layers by Mössbauer spectroscopy. For Fe layers with thickness below 16 Å, the Mössbauer spectra show always the presence of two ferromagnetic phases with high-spin state. In the range between 6 and 8 Å, also a ferromagnetic phase with low-spin state and a paramagnetic phase have been found. The evolution of the mean hyperfine field of the ⁵⁷Fe nuclei is used to study the Fe growth. A structural FCCBCC phase transition is found to begin with an iron thickness of 8 Å. The easy direction of the magnetization is found out-of-plane for Fe interlayer with FCC structure, and perfectly in plane for Fe interlayer with BCC structure.     

Performance of the far‐IR beamline of the 6 MeV tabletop synchrotron light source

The performance of the far‐infrared (FIR) beamline of the 6 MeV tabletop synchrotron light source MIRRORCLE‐6FIR dedicated to far‐infrared spectroscopy is presented. MIRRORCLE‐6FIR is equipped with a perfectly circular optical system (PhSR) placed around the 1 m‐long circumference electron orbit. To illustrate the facility of this light source, the FIR output as well as its spectra were measured. The optimum optical system was designed by using the ray‐tracing simulation code ZEMAX. The measured FIR intensity with the PhSR in place is about five times higher than that without the PhSR, which is in good agreement with the simulation results. The MIRRORCLE‐6FIR spectral flux is compared with a standard thermal source and is found to be 1000 times greater than that from a typical thermal source at ～15 cm^?1. It is also observed that the MIRRORCLE‐6FIR radiation has a highly coherent nature. The broadband infrared allows the facility to reach the spectral range from 10 cm^?1 to 100 cm^?1. MIRRORCLE‐6FIR, owing to a large beam current, the PhSR mirror system, a large dynamic aperture and small ring energy, can deliver a bright flux of photons in the FIR/THz region useful for broadband spectroscopy.     

A Mössbauer effect study of structural ordering in rapidly quenched Fe–Ga alloys

Samples of Fe_100−xGa_x (x=8.3, 17.9, 20.5 and 23.3) were prepared by rapid solidification from the melt using a single Cu roller. X-ray diffraction studies of all samples showed them to be single phase with the disordered BCC structure. No evidence of superlattice reflections from D0₃ ordering was observed for any of the samples. Room-temperature ⁵⁷Fe Mössbauer effect spectra indicated that all samples were ferromagnetically ordered. Spectra were fit to distributions of hyperfine fields. The x=8.3 sample showed a hyperfine field distribution that was single peaked and indicated a reasonably random distribution of local Fe environments. The x=17.9 and 20.5 samples showed hyperfine field distributions that were bimodal and indicated two distinct local Fe environments. The x=23.3 sample showed three distinct field components. It is suggested that the x=8.3, 17.9 and 20.5 alloys are primarily a disordered BCC phase. The x=8.3 alloy shows a small amount of short-range Ga–Ga pairing, while this short-range pairing is significantly greater in the x=17.9 and 20.5 alloys. The three field components in the x=23.3 alloy correspond well to the two sites associated with the D0₃ phase and a third component corresponding to a remaining L1₂ phase suggesting the presence of at least short-range D0₃ clustering in this alloy.