Mössbauer study of a novel binuclear Fe(II/III) delocalized-valence compound

In this paper, we briefly summarize the main conclusions of the Mössbauer analysis of [L₂Fe₂(-OH)₃] (ClO₄)₂·2CH₃OH·2H₂O with L=N,N',N"-trimethyl-1,4,7-triazacyclononane, a novel dimeric iron compound, which possesses a central exchange-coupled delocalized-valence Fe(II/III) unit. The complete delocalization of the excess electron in the dimeric iron center is concluded from the indistinguishability of the two iron sites in Mössbauer spectroscopy. The magnetic Mössbauer spectra imply a system spinS _t=9/2 for the dimer in its ground state. The values for hyperfine and spin-Hamiltonian parameters, obtained from simulations of the Mössbauer spectra, are =0.74 mms^–1, E _Q=–2.14 mms^–1,A =–10.6 T,A =–13.5 T andD=1.8 cm^–1. The system spinS _t=9/2 is interpreted to be a consequence of double-exchange coupling.     

Mössbauer study of FINEMET with different permeability

Stress field and magnetic field annealed FINEMET ribbons were investigated by ⁵⁷Fe Mössbauer spectroscopy, magnetic and XRD methods. The change in relative areas of the 2nd and 5th lines in the Mössbauer spectra indicated significant variation in magnetic anisotropy due to the different annealing. High velocity resolution Mössbauer spectroscopy was also used to control the model applied for the evaluation of Mössbauer spectra. A correlation was found between the permeability and the magnetic anisotropy of the annealed FINEMET samples. This can be applied to predict production parameters of FINEMET ribbons with more favorable soft magnetic properties for technological applications.     

Mössbauer study of tektites

Room temperature ⁵⁷Fe Mössbauer spectroscopy has been used to investigate the structural and oxidation state of Fe in tektites from different strewn fields. Spectra have been analyzed in terms of two quadrupole splitting distributions corresponding to Fe^3?+? and Fe^2?+?. All tektites show similar distribution of quadrupole splitting. Each distribution has one peak. The Fe^2?+? sites show a narrow region of Mössbauer line shift (δ) and quadrupole splitting (ε), δ?= 1.02–1.10 mm/s and ε?= 0.85–1.00 mm/s relative to α-Fe. These values have been assigned to intermediate coordination between tetrahedral and octahedral. The Fe^3?+? sites show wider regions of hyperfine parameters: δ?= 0.25–0.45 mm/s and ε?= 0.65–0.90 mm/s. The Fe^3?+?/Fe^2?+? ratio was found to be 0.05–0.15.     

Mössbauer spectroscopy of single-crystal LiNbO3:Fe(III)

Mössbauer spectra of LiNbO₃: Fe(III)-monocrystals in external magnetic fields of 0.3–7T with various configurations of the -direction, c-axis of the crystal, and the magnetic field direction are interpreted by means of a spin Hamiltonian. A consistent set of hyperfine and crystal-field parameters could be least squares fitted for all spectra. Arguments that Fe(III) substitutes Nb(V) are given.Work partly performed in ICEx/UFMG, Depto. de Fisica, Belo Horizonte, Brasil     

Mössbauer spectra of iron (III) sulfide particles

Trivalent iron sulfide (Fe₂ S ₃) particles were synthesized using a modified polyol method. These particles exhibited a needle-like shape (diameter =?10-50 nm, length =?350-1000 nm) and generated a clear XRD pattern. Mössbauer spectra of the product showed a paramagnetic doublet at room temperature and distributed hyperfine magnetic splitting at low temperature. The Curie temperature of this material was determined to be approximately 60 K. The data suggest that the Fe₂ S ₃ had a structure similar to that of maghemite (γ-Fe₂ O ₃) with a lattice constant of a =?10.6 Å. The XRD pattern calculated from this structure was in agreement with the experimental pattern and the calculated hyperfine magnetic field was also equivalent to that observed in the experimental Mössbauer spectrum.     

Auto-combustion synthesis,Mössbauer study and catalytic properties of copper-manganese ferrites

Spinel ferrites with nominal composition Cu _0.5Mn _0.5Fe ₂ O ₄ and different distribution of the ions are obtained by auto-combustion method. Mössbauer spectroscopy, X-ray Diffraction, Thermogravimetry-Differential Scanning Calorimetry, Scanning Electron Microscopy and catalytic test in the reaction of methanol decomposition is used for characterization of synthesized materials. The spectral results evidence that the phase composition, microstructure of the synthesized materials and the cation distribution depend on the preparation conditions. Varying the pH of the initial solution microstructure, ferrite crystallite size, cation oxidation state and distribution of ions in the in the spinel structure could be controlled. The catalytic behaviour of ferrites in the reaction of methanol decomposition also depends on the pH of the initial solution. Reduction transformations of mixed ferrites accompanied with the formation of Hägg carbide χ-Fe ₅ C ₂ were observed by the influence of the reaction medium.     

Reduction of amorphous Fe(III)-hydroxide by binary microbial culture, a Mössbauer study

Mössbauer investigations between 4.5 and 300 K of iron minerals formed during the growth of the binary culture containing two anaerobic alkaliphilic bacteria-dissimilatory iron-reducing Geoalkalibacter ferrihydriticus (strain Z-0531) and organotrophic Anaerobacillus alkalilacustre (strain Z- 0521), have been carried out. Mannitol (2 g/l) as the sole substrate with amorphous Fe(III) hydroxide at final concentration 10 or 100 mM were added to the mineral medium. The formation of siderite and probable magnetite or a mixture of magnetite and maghemite were observed.     

Mössbauer and EPR study of nitrosyl hemoglobin

Nitrosyl hemoglobin was prepared by bubbling fresh⁵⁷Fe-enriched rat hemoglobin with NO. S- and X-band EPR spectra at 77 K are typical for anS=1/2 system with an anisotropicg-tensor and exhibit hyperfine interactions of¹⁴N with the electronic spin. Mössbauer spectra at 4.2 and 100 K consist of a superposition of spectra from high- and low-spin Fe(III), deoxygenated hemoglobin and a component corresponding toS=1/2,g=2, hyperfine constantsA _xx /g _{n n} =A _yy /g _{n n} =–19.6 T,A _zz /g _{n n} =6.8 T, quadrupole splitting E _Q=1.5 mm s^–1, isomer shiftI _s=0.42 mm s^–1 and linewidth 0.4 mm s^–1. The spin-lattice relaxation rate at 100 K is <2×10⁶ s^–1.     

Mössbauer spectroscopic study of the early crystallization stage of iron(III) hydroxide particles

Mössbauer spectroscopy was used to investigate the early aging stage of iron(III) hydroxide sols prepared by oxidation of Fe(CO)₅ in ethanolic solution, followed by vacuum drying at room temperature. One sample was composed of amorphous particles, while two other samples were partially crystallized, either as a result of solvent change or of spontaneous aging. The main results of Mössbauer measurements in the 80–320 K temperature range are: (a) partially crystallized particles exhibit a strong, S-shaped temperature dependence of the quadrupole splitting, in contrast to a weak and linear variation for amorphous particles; (b) the recoilless fraction temperature dependence is affected by vibration of the particles as a whole, with an effective force constant which is smaller for crystallized particles than for amorphous ones. Furthermore, the former exhibit anf-factor discontinuity near 0°C, which is attributed to melting of a surface layer built up during the crystallization process.     

Mössbauer study of iron removal in a montmorillonite

⁵⁷Fe Mössbauer spectroscopy in conjunction with atomic absorption spectrometry and X-ray powder differaction analyses have been used to study the iron present in a montmorillonite prior to and after different successive stages of two deferration processes. Fe³⁺ ions occupy mainly octahedrical M(2) sites in the mineral structure; no impurities of iron oxides were detected. The quite efficient deferration by HCl refluxing produced a substantial alteration of lamellar structure of montmorillonite, whilst dithionite/citrate treatment did not induce severe structural changes but had low iron removal efficiency.     

Mössbauer study of Slovak meteorites

⁵⁷Fe Mössbauer spectroscopy was used as an analytical tool in the investigation of iron containing compounds of two meteorites (Rumanová and Ko?ice) out of total of six which had fallen on Slovak territory. In the magnetic fraction of the iron bearing compounds in the Rumanová meteorite, maghemite, troilite and Fe-Ni alloy were identified. In the non-magnetic fraction silicate phases were found, such as olivine and pyroxene. The paramagnetic component containing Fe^3?+? ions corresponds probably to small superparamagnetic particles. The Ko?ice meteorite was found near the town of Ko?ice in February 2010. Its magnetic fraction consists of a Fe-Ni alloy with the Mössbauer parameters of the magnetic field corresponding to kamacite α-Fe(Ni, Co) and troilite. The non-magnetic part consists of Fe^2?+? phases such as olivine and pyroxene and traces of a Fe^3?+? phase. The main difference between these meteorites is their iron oxide content. These kinds of analyses can bring important knowledge about phases and compounds formed in extraterrestrial conditions, which have other features than their terrestrial analogues.     

Mössbauer study of Hungarian phlogopites

Ultramafic xenoliths of mantle origin occur in Hungarian Cretaceous lamprophyres. The aim of the present work was to determine the iron positions and their occupancy in phlogopites originated from ultramafic xenoliths by the help of Mössbauer spectroscopy. On the basis of the evaluation of the Mössbauer spectra Fe _M1 ²⁺ , Fe _M2 ²⁺ , Fe _M2 ³⁺ and Fe _M1 ³⁺ (or in some cases Fe_tet) octahedral and tetrahedral iron sites were identified in the samples. Quantitative analysis was performed for all of the iron sites. We have observed large differences between the Fe²⁺/Fe³⁺ ratio in samples originated from 120–150 km deepness, which phlogopites having been existed at different erosion circumstances. We have found a significantly higher Fe²⁺/Fe³⁺ ratio in phlogopites which had been solidified in 120–150 km depth from the surface of Earth 70–100 million years ago, than those had been crystallized in 60–80 km deepness.     

Mössbauer study of Brazilian soapstone

Steatite mineral rocks, soapstone, have been studied by X-ray diffraction, optical microscopic analysis (modal analysis), electron probe micro analysis and Mössbauer spectroscopy for characterization, mineral percentages and chemical composition. Mössbauer spectra show both, magnetic interactions corresponding to magnetite and doublets corresponding to talc. chlorite, dolomite and tremolite. The temperature dependence of the quadrupole splitting in dolomite has been explained in terms of crystal field interaction.     

Mössbauer study of natural wolframites

Natural Wolframite, (Fe _x Mn_1?x )WO₄ withx=0.95 to 0.41, obtained from seven different sites of two quartz-wolframites deposits of Degana and Sirohi in Rajasthan. India, have been studied by Mössbauer spectroscopy down to 20 K. X-ray diffraction studies with a monochromatic Cu radiation (λK_a-1.5405 Å), were carried out to determine the value ofx. The Mössbauer spectra of all seven samples were recored at 300, 200, 100, 50, 40, 30 and 20 K, and were least square fitted for different sites. The Mössbauer parameters are attributed to a high spin ferrous ion in a quite distorted octahedral symmetry, and only one sextet has been resolved below transition temperature.     

Mössbauer study of spin structure transformation from an incommensurate to a commensurate state

We present crystallographic and magnetic properties of NiCr_1.98 ⁵⁷Fe_0.02O₄ by using X-ray diffractometry (XRD), vibrating sample magnetometry (VSM), and Mössbauer spectroscopy. The lattice constants a₀ were determined to be 8.318 Å. The ferrimagnetic Neel temperature (T _N) for NiCr_1.98 ⁵⁷Fe_0.02O₄ is determined to be 90 K. The Mössbauer absorption spectra for all chromites at 4.2 K show two well developed sextets superposed with small difference of hyperfine fields (H _hf) caused by Cr^3?+? ions in two different magnetic sites. The values of the isomer shifts show that the charge states of Fe are Fe^3?+? for all temperature range. Ni-chromites Mössbauer spectra below T _N present aline broadening due to a Jahn–Teller distortion and show that spin structure behavior of Cr ions change from an incommensurate to a commensurate state.