Mössbauer spectroscopy in studies of photosynthesis

Photosynthesis is a process occurring in certain species of bacteria, algae and higher plants. It transforms solar energy into various forms of energy-rich organic molecules. Photosystem II (PSII) is the “heart” of the photosynthetic apparatus because it delivers electrons and protons for further steps of the light-driven phases of photosynthesis. There are two enigmatic iron binding structures within the core of photosynthetic apparatus, which play an important role in the electron transfer within PSII. Many investigations focus on the determination of their function which is the key to the understanding of the molecular mechanism of the energy and electron transfer within PSII. Among many methods used in this research field, the Mössbauer spectroscopy is a unique one, which gives the possibility to study changes of the valence and spin states of those two iron sites and the dynamical properties of their protein matrix in the presence of various physiological and stress conditions.     

Mössbauer spectroscopy of Al substituted Fe in holmium iron garnet

A Mössbauer spectroscopy study was made on Ho₃Fe_5-xAl_xO₁₂ (x=0.0, 0.05, 0.7). X‐ray diffraction patterns indicate that the samples with x=0.0 and 0.05 have the garnet structure, while the sample with x=0.7 has an additional noncubic structural phase. The room temperature spectrum for samples with x=0.0 and 0.05 consists of two magnetic components corresponding to the octahedral and tetrahedral sites with hyperfine magnetic fields (B_hf) of 50 T and 40 T, respectively. For x=0.7 we observe a new magnetic component with B_hf= 45 T, a reduction in the intensity and broadening of the tetrahedral component, and the evolution of a nonmagnetic central component. These variations are evidently due to the addition of aluminium to the system. At liquid nitrogen temperature the samples with x=0.0 and 0.05 are nearly identical. It was also observed that the increase in B_hf for the octahedral site is smaller than that for the tetrahedral site as the temperature is lowered to 80 K.     

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.     

Mössbauer spectroscopy in the investigation of new mineral–related materials

New materials based on the composition of the mineral schafarzikite, FeSb $_{2}\textit {O}_{4}$ , have been synthesised. $^{57}$ Fe- and $^{121}$ Sb- Mössbauer spectroscopy shows that iron is present as Fe $^{2+}$ and that antimony is present as Sb $^{3+}$ . The presence of Pb $^{2+}$ on the antimony sites in materials of composition FeSb $_{1.5}$ Pb $_{0.5}\textit {O}_{4}$ induces partial oxidation of Fe $^{2+}_{}$ to Fe $^{3+}$ . The quasi-one-dimensional magnetic structure of schafarzikite is retained in FeSb $_{1.5}$ Pb $_{0.5}\textit {O}_{4}$ and gives rise to weakly coupled non-magnetic Fe $^{2+}$ ions coexisting with Fe $^{3+}$ ions in a magnetically ordered state. A similar model can be applied to account for the spectra recorded from the compound Co $_{0.5}$ Fe $_{0.5}$ Sb $_{1.5}$ Pb $_{0.5}\textit {O}_{4}$ .     

Mössbauer study of cubic FeGe

The cubic structure of FeGe has been examined in the temperature range 80 – 300°K. The isomer shift and the quadrupole splitting suggest a Fe³⁺ state. A magnetic transition was found slightly above 273°K.     

Mössbauer spectroscopy of Co2Mn1 − x Fe x Al

⁵⁷Fe Mössbauer spectroscopic studies of Co₂Mn_1???x Fe _x Al based Heusler compounds are presented. The cubic structure type was found for all samples of the series in XRD studies. However, a mixture of the cubic B2 and L2₁ structure types are not unambiguously distinguished by XRD. The present study gives evidence for a mixture of the L2₁ structure with additions of a large amount of B2 like disorder. The isomer shifts and hyperfine magnetic fields on ⁵⁷Fe atoms are compared with theoretical values from CPA calculations.     

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.     

A dilute-limit heat of solution of molybdenum in iron studied with 57Fe Mössbauer spectroscopy

The room temperature Mössbauer spectra of ⁵⁷Fe were measured for iron-based solid solutions Fe_1???x Mo _x with x in the range 0.01?≤?x?≤?0.05. The obtained data were analysed in terms of the binding energy E _b between two molybdenum atoms in the studied materials using the extended Hrynkiewicz–Królas idea. It was found that the energy is positive or Mo atoms interact repulsively. The extrapolated value of E _b for x?=?0 was used for computation of the dilute-limit heat of solution of Mo in Fe. The obtain result was compared with both, the corresponding values given in the literature which were calculated theoretically on the basis of the simple embedded-atom model, as well as with the value resulting from the cellular atomic model of alloys by Miedema. The comparison shows that our findings are in a qualitative agreement with the Miedema’s model predictions and they are at variance with the theoretical computations mentioned above.     

Mössbauer investigation of iron uptake in wheat

Iron uptake and distribution in wheat roots were studied with ⁵⁷Fe Mössbauer spectroscopy. Plants were grown both in iron sufficient and in iron deficient nutrient solutions. Mössbauer spectra of the frozen iron sufficient roots exhibited three iron(III) components with the typical average Mössbauer parameters of δ?= 0.50 mm s^???1, Δ?= 0.43 mm s^???1, δ?= 0.50 mm s^???1, Δ?= 0.75 mm s^???1 and δ?= 0.50 mm s^???1, Δ?= 1.20 mm s^???1 at 80 K. These doublets are very similar to those obtained earlier for cucumber [0], which allows us to suppose that iron is stored in a very similar way in different plants. No ferrous iron could be identified in any case, not even in the iron deficient roots, which confirms the mechanism proposed for iron uptake in the graminaceous plants.     

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.     

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 polarized monochromatic radiation

The possibility of carrying out Mössbauer experiments with monochromatic linearly polarized radiation is demonstrated. Mössbauer spectra of a transversely magnetized iron foil for radiation polarized parallel and perpendicular to the magnetization are given.     

Investigation of the cation distribution in perovskite-like oxides with Mössbauer spectroscopy

Complex perovskite-like oxides, such as LnFe_2/3Mo_1/3O₃ orthoferrites, Ln_8?ySr_yCu_8?xFe_xO₂₀ (8-8-20), Pr₄BaCu₄FeO_13-δ(4-1-5), YBa_2-yLa _y Cu_3-xFe _x O_7-δ and Y_1-yCa _y Ba _y La _y Cu_3-xFe _x O_7-δ (1-2-3), are studied by means of Mössbauer spectroscopy. At room temperature, the spectra of the orthoferrites contain only magnetic components. The spectra of the 1-2-3 compounds contain only magnetically disordered components: iron atoms substitute for copper at Cu(1) sites, taking various configurations: planar squares, quadratic pyramids, and octahedra. Cuprates 8-8-20 and 4-1-5 have a wide diversity of spectra. In the 8-8-20 oxides, a phase related to the pyramidal environment of the iron cations is present at any iron concentration. In all the perovskites, iron cations become magnetically ordered only at octahedral sites of the structure.     

Methodological problems of quantitative analysis in Mössbauer spectroscopy

The results from research into the effect of different factors on errors in quantitative determination of the phase composition of studied substances by Mössbauer spectroscopy ion absorption are presented, and ways of using them are suggested. The effectiveness of the suggested methods is verified by an example of analyzing standard and unknown compositions.     

Fe mineralogy of rocks from the Vredefort impact structure investigated with Mössbauer spectroscopy

The Vredefort impact structure in South Africa is the largest and oldest remnant impact structure on Earth. Observations from above the crater reveal lower than average magnetic field intensities, but the rocks in the crater have been shown to possess much higher magnetic intensities than the regional average that varies on a centimeter scale. Various mechanisms, including the presence of single domain magnetite structures, have been proposed for this anomaly. Mössbauer spectroscopy has been applied to study the Fe-mineralogy of samples from near the centre of the Vredefort crater. Transmission Mössbauer measurements on bulk and microtomics sections of samples showed that the magnetic minerals were magnetite and hematite, and we suggest that oxidation of olivine during the impact is responsible for the magnetic properties of the rocks.     

Gamma-X-ray coincidence Mössbauer emission spectroscopy on57Co/CoO

The time integral Mössbauer emission spectrum of a⁵⁷Co/Co_1–x O source (x 10^–5) at RT consists of two single Lorentzian lines of an Fe²⁺ (76%) charge state and an Fe³⁺ (24%) aliovalent charge state. The spectrum measured by -X-ray coincidence spectrpscopy shows the same fraction of the aliovalent charge state, contrary to the expectation derived from the competing acceptor model as successfully applied by Tejada and Parak [1], who could explain the dependence of the formation of aliovalent charge states after the nuclear transformation on the stoichiometric parameterx. The consequences of this unexpected behaviour for the competing acceptor model are discussed.     

Mössbauer spectroscopy with the 93 keV-resonance in67Zn

The procedures and results of high resolution Mössbauer experiments performed with the 93.3 keV resonance in absorbers of⁶⁷ZnO,⁶⁷ZnS (both wurtzite and sphalerite structures),⁶⁷ZnSe,⁶⁷ZnTe and⁶⁷ZnF₂ are reported. An essentially linear dependence between the isomer shift and the Pauling electronegativity of the ligands was found. A value of r ²=+11×10^–3 fm² is estimated. The Mössbauer parameters for both ZnS structures are equal within present limits of error. In particular, no quadrupole interaction was observed in the wurtzite modification. This indicates a nearly identical local symmetry at the Zn site in the two ZnS structures.Work supported by the Bundesministerium für Forschung und Technologie, Federal Republic of Germany and the Kernfor-schungszentrum Karlsruhe     

Mössbauer investigation of temperature transformations in bacterial ferrihydrite

Ferrihydrite nanoparticles formed as a result of the microorganism activity have been studied using Mössbauer spectroscopy, X-ray powder diffraction analysis, and X-ray fluorescence analysis. Three positions of trivalent iron with nonoverlapping ranges of quadrupole splittings have been revealed in bacterial ferrihydrite: QS{Fe³⁺(1)} = 0.49–0.83 mm/s, QS{Fe³⁺(2)} = 0.84–1.10 mm/s, and QS{Fe³⁺(3)} = 1.25–1.73 mm/s. It has been experimentally demonstrated that the Fe³⁺(3) positions are the centers of nucleation of the hematite phase in the course of heat treatment.