Position — Sensitive single-wire proportional counter for conversion electron Mössbauer spectroscopy

A position-sensitive single-wire proportional counter for the INS 2 air-core spectrometer has been improved to take conversion electron Mössbauer spectrum as a function of electron energy with a multichannel mode. The position resolution at 13.6 keV was found to become 1.6 mm with the counter gas pressure of 320 Torr. The position resolution was obtained as a function of energy between 7 and 60 keV for gas pressure of 40 Torr, 160 Torr and 320 Torr. The L, M and N conversion electron spectrum of the 14.4 keV transition in⁵⁷Fe was taken with the present system. Overall momentum resolution was found to be 0.23% for the L₁-line and 0.19% for the M₁ line.     

Depth selective conversion electron Mössbauer spectroscopy by use of a proportional counter

The depth selectivity of conversion electron Mössbauer spectroscopy by use of a proportional counter was studied in detail. For this purpose the pulse-height spectrum of conversion and Auger electrons emitted from a⁵⁷Fe absorber was measured at the resonance Doppler velocity. From the spectrum it is found that the energy settings of 2–5 keV, 6–9 keV and 11–14 keV are suitable for depth selective analysis.     

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.     

New relaxation model for superparamagnetic particles in Mössbauer spectroscopy

A new model is suggested for the relaxation in a system of superparamagnetic particles. The model takes into account the interparticle interaction and ensuing smearing of energy levels for each individual particle, such that the relaxation between the particle states with opposite directions of magnetic moment never occurs as a transition between the states of the same energy. This generalization of the relaxation model accounts for the diversity of relaxation Mössbauer absorption spectra, allowing all the nonstandard features that were observed previously in the experimental spectra of systems with small-sized particles to be described on a qualitative level.     

Mössbauer conversion electron studies of tantalum metal surface layers

Conversion electrons following the Mössbauer absorption of the 6.2 keV -rays of¹⁸¹Ta were observed in backscattering geometry. Mössbauer spectra for tantalum single crystal and foil surfaces (mean-depth 330 Å) are compared with normal transmission spectra for tantalum foils (bulk). While no broadening of lines is observed for carefully polished single crystal furfaces, foil surfaces show considerably broader lines than bulk spectra. The linewidth and isomer shift indicate an increase of the concentration of absorbed residual gases at the foil surfaces. The observed dispersion term arising from the interference between photo- and conversion electrons for this E1-transition, depends only on the absorber thickness.     

A novel type of depth-selective Auger electron Mössbauer spectroscopy

The utility of parallel-plate avalanche detectors for depth-selective Auger electron Mössbauer spectroscopy is demonstrated for the 24 keV transition of¹¹⁹Sn. Possible developments and applications of this technique to other Mössbauer isotopes are discussed.     

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 spectroscopy study of interfaces for spintronics

The submonolayer sensitivity and element-specificity of conversion electron Mössbauer spectroscopy, combined with the use of ⁵⁷Fe enriched tracer layers, enable to carefully investigate thin films and interfaces at the atomic-scale. This paper reports on the main achievements we obtained so far in the study of structural, chemical, and magnetic properties of a variety of interfaces between oxides and Fe-based films having potential interest in the field of spintronics.     

67Zn Mössbauer spectroscopy

The 93.31-keV Mössbauer resonance in⁶⁷Zn is used to determine tiny changes of the transition energy. We first report on a gravitational redshift (GRS) experiment with⁶⁷GaZnO single crystal source and⁶⁷ZnO powder as absorber. The results on the GRS show that solid state effects which are difficult to control experimentally, in particular the extreme sensitivity of the electric field gradient tensor (efg) in⁶⁷ZnO to small external pressure, finally limit the accuracy in determining the GRS. The resonance has been further employed to investigate solid state properties of⁶⁷ZnO with high precision. At large pressures⁶⁷ZnO exhibits a phase transition from hep (wurtzite) to fcc (NaCl) structure. The changes of the efg and of the s-electron density θ(0) at the⁶⁷Zn nucleus with reduced unit cell volume show that covalency of the Zn-O bond plays and essential role. We have performed self-consistent Hartree-Pock cluster calculations to describe the experimental changes of θ(0) in detail.     

Mössbauer spectroscopy at ISOLDE

Applications of radioactive ion beams produced at the ISOLDE facility for Mössbauer studies of probe atoms in solids are presented. Examples are given for a site-selective incorporation on different substitutional sites in compound semiconductors by ion implantation and thermal annealing of the radiation damage resulting from the implantation. The interactions of the probe atoms with lattice defects created in the implantation process have been studied to elucidate likely causes for the site-selective implantation mechanism. The technique has enabled to determine the electronic densities at electrically active substitutional probe atoms, having shallow donor or acceptor states as well as states deeper in the band gap. The results are in good agreement with theoretical results from local density calculations. Methodological aspects of the Mössbauer emission techniques employed at ISOLDE are compared to alternative accelerator based techniques and the consequences of the application of different precursor isotopes to the ⁵⁷Fe Mössbauer isotope are treated in detail for ⁵⁷Fe in silicon. Finally, results obtained for the magnetic hyperfine interactions of 5 sp impurities associated with vacancies in ferromagnetic metals are discussed.     

Mössbauer spectroscopy in catalysis

Application of in situ Mössbauer spectroscopy for studying catalysts and catalytic processes is discussed. Examples are presented to illustrate the potentials of the method by describing studies on supported heterogeneous catalysts performed with ¹¹⁹Sn and ⁵⁷Fe spectroscopies in cases with certain metals and alloys, oxides and porous substances. The results are interpreted in comparison to the catalytic performance.     

Design of a conversion electron Mössbauer spectrometer based on an electron multiplier. Evaluation of the mean-escape-depth of the detected signals

A Conversion Electron Mössbauer Spectrometer to be used for the characterization of Fe-containing metal surfaces was designed and installed in an Ultra High Vacuum chamber. The design is based in the use of a Channeltron electron multiplier for the detection of electrons emerging from the sample after an incident γ-Ray is absorbed by resonant nuclear excitation. Using a Monte Carlo simulation for electron trajectories in solids the mean-escape-depth of the detected Mössbauer signal from a metallic iron sample was estimated to be 80 nm, assuming that the main signals being detected correspond to the Fe(M), Fe(L) and Fe(K) conversion electrons as well as the Fe(KLM), Fe(KLL) and Fe(LMM) Auger electrons. The sensitivity to the surface region was also estimated experimentally by acquiring Mössbauer spectra from a series of Fe films of different thickness deposited by magnetron sputtering on 304 stainless steel substrates.     

Prospects for emission Mössbauer spectroscopy in chemical investigations

Emission Mössbauer spectroscopy is a radiochemical method for investigating materials and the consequences of nuclear transformations taking place in them. Isotopes are traditionally used as structural probes, and the sensitivity of the method is 2–3 orders of magnitude higher than that of absorption Mössbauer spectroscopy. The elements of Mössbauer isotopes with parent nuclei that undergo electron capture or a converted isomeric transition (i.e., lead to high Auger ionization) are the best-studied elements. The electron processes that accompany ionization and their effect on the state of daughter Mössbauer atoms in qualitatively different compounds, from elementary oxides, superconductors, insulators and magnetics to sophisticated bioorganic complexes, are considered.     

A versatile gas-flow proportional counter for Mössbauer spectroscopy

We discuss the need for neutral atom traps instead of atomic beams for the high-precision spectroscopic comparison of anithydrogen and hydrogen. We also describe recent proposals and advances towards a new trap for hydrogen and briefly discuss traps for antihydrogen.     

A simple six-input multichannel system for Mössbauer spectroscopy

A multichannel system for Mössbauer spectroscopy was developed and is presented. The system, constructed as an NIM module, is connected to the DMA port of an ATARI ST computer and can be used for six detectors simultaneously, thus allowing the operation of simultaneous triple radiation Mössbauer spectroscopy (STRMS). The multichannel system is explained and its capabilities are demonstrated.     

Mössbauer spectroscopy in physical metallurgy

In this anniversary contribution the natural and intimate match making which occurs between the two star performers-⁵⁷Fe in Mössbauer spectroscopy and iron in physical metallurgy—is described by selecting typical examples reflecting the author's interest: phases, f.c.c. -Fe, defects, diffusion and amorphous metals.     

Mössbauer spectroscopy of zirconium alloys

Mössbauer investigations of zirconium alloys were examined. Data about the chemical state of iron atoms in the zirconium alloys of different composition has been provided. Mössbauer spectroscopy revealed that small quantities of iron in binary zirconium alloy are in the solid solution α-Zr (up to 0.02 wt.%). Different iron atoms concentration and thermo-mechanical treatments may lead to formation the intermetallic compounds Zr₃Fe, Zr₂Fe, ZrFe₂. Adding tin atoms does not affect the formation and shape of Mössbauer spectra of these compounds. Adding Cr and Nb atoms makes significant changes in the shape of Mössbauer spectra and leads to the formation of complex intermetallic compounds. Adding Cu and W atoms, the shape of the binary alloys spectra (Zr-Fe) remains unchanged, but a change in the temperature dependence behavior of the spectral parameters occurs and also, changes to the properties of the alloys.     

Mössbauer spectroscopy with actinide elements

Although formally equivalent to the lanthanide (4f) elements, the light actinides show a much more varied behaviour due to the larger spatial extent and ionizability of the 5f electrons. The application of Mössbauer spectroscopy for the determination of electronic properties of the actinides is outlined. Emphasis is put on high pressure Mössbauer experiments using the 60 keV transition in²³⁷Np to study questions of delocalization of 5f electrons.Work performed under the auspices of the Bundesministerium für Forschung und Technologie, Federal Republic of Germany.     

Mössbauer spectroscopy in molecular magnetism

The aim of this paper is to highlight some selected research activities on molecular magnetic materials using Mössbauer spectroscopy as a technique carried out in our laboratory in recent years. The first part of the present article is devoted to the studies of the various magnetic interactions, metal-to-metal electron-transfer phenomenon, glass transition occurring in molecular magnetic materials, whereas the second part deals with the iron(II) high spin (S = 2)–low spin (S = 0) transition phenomenon occurring in some isoxazole ligand based iron(II) compounds as examples with unusually complicated spin transition behaviour. Also, an example of a dinuclear a spin crossover compound of iron(II) is described, where Mössbauer spectroscopy has most convincingly unraveled the mechanism of the spin transition process. Finally, an example from our most recent studies of spin crossover materials exhibiting both thermal spin crossover and liquid crystalline properties in the same temperature interval near room temperature will be presented.