Magnetic properties and 57Fe Mössbauer effect in Lu6Fe23 and Lu6Fe23H8

Hydrogen absorption in the cubic compound Lu₆Fe₂₃ ($\text{a}\text{= 11.936}\text{A}\text{?}$) leads to a ternary hydride of the composition Lu₆Fe₂₃H₈ ($\text{a}\text{= 12.072}\text{A}\text{?}$). The H₂ take-up causes a slight increase in the saturation magnetization corresponding to an increase in Fe moment from 1.54 /u_B to 1.64/u_B per atom. The hydrogen absorption did not lead to a substantial change in the linewidth of the ⁵⁷Fe Mössbauer spectrum. On the basis of the Mössbauer data it was inferred that the H atoms occupy the f-type interstitial holes characterized by a tetrahedron formed of three Lu atoms and one Fe atom. The decrease in hyperfine field upon charging was correlated with an increase in Curie temperature.     

Transfert électronique d'intervalence entre sites inéquivalents: Étude de CaFe3O5 par spectrométrie Mössbauer

As in magnetite Fe₃O₄, calcium ferrite CaFe₃O₅ is an oxide in which electron transfer occurs between the iron ions ($\text{Fe}{}^{\mathrm{3+}}\text{Fe}{}^{\mathrm{2+}}\text{= 2}$). This intervalence exchange process has been studied by ⁵⁷Fe Mössbauer spectroscopy and by electrical conductivity measurements. In CaFe₃O₅, the Fe³⁺ and Fe²⁺ ions occupy different crystallographic sites and have a deformed octahedral coordination. Each Fe²⁺O₆ octahedron shares an edge with two Fe³⁺O₆ octahedra. In the antiferromagnetic region (T_N = 282 ± 2 K), the Fe³⁺ and Fe²⁺ ions are well differentiated. Thermally-activated electron transfer is observed above t_n, in the paramagnetic region and is well characterized by the Mössbauer spectra. These are analyzed using the hypothesis of an electron jump limited to a trimer Fe³⁺Fe²⁺Fe³⁺ which leads to a relaxation time of 180 ns at 298 K and 80 ns at 400 K. Within this temperature interval, the process follows the Arrhenius law with an activation energy of 0.10 eV. Electrical conductivity measurements lead to similar results with an activation energy of 0.09 ± 0.02 eV.     

The coordination of Co2+ions in Co substituted magnetites,Fe3−xCoxO4, with x⩽0.04

⁵⁷Fe Mössbauer spectra at room temperature, both with and without external magnetic field, indicate that Co²⁺ ions in Co_xFe_3?xO₄spinels (x?0.04) are situated on the octahedral B sites. The Mössbauer parameters are listed and the existence of unpaired Fe³⁺ ions is evidenced.     

Determination of the recoilless-fraction for57Fe in Fe3O4 by the Mössbauer Faraday effect

We have observed the Mössbauer Faraday effect in nonstoichiometric Fe₃O₄ by using a Mössbauer polarimeter. Experimental results demonstrated that electronic hopping above the Verwey temperature between Fe²⁺?Fe³⁺ ions on the octahedral sites is a localized phenomenon only and the recoilless fractions of⁵⁷Fe nuclei in Fe_3?vO₄ (v=0.02) are 0.71 for A sites and 0.62 for B sites, respectively.     

Magnetic insulator glasses

An outline is given of the use of Mössbauer spectroscopy as a probe of the amorphous structure and magnetic coordination in magnetic insulator glasses. Using the⁵⁷Fe Mössbauer resonance as an example in the context of amorphous ferric oxides and fluorides, the manner in which both paramagnetic and hyperfine-field-split spectra can be analyzed is presented. Emphasis is given to the information contained in Mössbauer lineshapes and linewidths in addition to the more obvious line-position data. A number of general findings are set out for ferric speromagnetics with particular references to Mössbauer studies of amorphous Fe₂O₃, Y₃Fe₅O₁₂ (YIG), FeF₃ and NaFeF₄.     

151Eu and57Fe Mössbauer effect studies of magnetic interactions in europium transition element oxides solution

The solid state solutions of europium transition element oxides Eu (Fe0.8M0.2)O₃ (M=Sc,Cr,Mn,Co) are synthesized. The X-ray diffraction of the compound shows that all the compounds possess the perovskite structures. Both the¹⁵¹Eu Mössbauer spectra and the⁵⁷Fe Mössbauer spectra are measured. The hyperfine magnetic field and non-axisymmetric electric field gradient are observed in the¹⁵¹Eu Mössbauer spectrum. The⁵⁷Fe Mössbauer spectrum shows that there are four components of hyperfine fields corresponding to four kinds of different neighbours of the Fe ion.     

Magnetic interactions between Fe(III) ions in the solid solutions CuM1 − xFexS2 (M = Al,Ga, In) and AgM1 − xFexO2 (M = Al,Ga).

Magnetic properties of CuM_{1 ? x}Fe_xS₂ (M = Al, Ga, In) and β-AgM_{1 ? x}, Fe_xO₂ (M = Al, Ga) solid solutions have been studied by Mössbauer spectroscopy (only on CuGa _{1 ? x}Fe_xS₂), magnetization measurements and EPR spectroscopy.In the structures studied all ions have tetrahedral co-ordination.The magnetic interactions between Fe(III) ions are shown to be very strong for nn sites ($\text{J}\text{k}$～100 K). More distant exchange interactions are found to fall off rather slowly as the distance between Fe(III) ions increases and are suggested to depend essentially on the number of bonds traversed.     

Preparation and Mössbauer spectra of CoV2O4 spinel doped with Fe2+ on tetrahedral sites

Co²⁺_0.98Fe²⁺_0.02Fe³⁺_?V³⁺_2-? 04 (?? 0.001) was obtained from a sample containing the iron dope mainly in the trivalent state, by reducing it at 910°C in a CO₂/CO atmosphere. Mössbauer spectra of ⁵⁷Fe at the tetrahedral site were taken between 5 and 300 K. Below the Curie temperature (143 K) there is a magnetically induced electric field gradient eQV_zz and a reduction of the hyperfine field H_hf. Values at 5 K are H_hf=141 kG and eQV_zz=5.74 mm/s. The effective splitting of the Fe²⁺⁵E ground-state doublet, as estimated from the temperature dependence of eQV_zz and H_hf, is $\text{2q}\text{δ}\text{/k = 28 K}$. It is derived that in these oxides the coupling of the electronic ⁵E states to local Jahn-Teller active E-modes of vibration is stronger than in comparable sulphides.     

57Fe Mössbauer study of new multiferroic AgFeO2

The present work reports results of the ⁵⁷Fe Mössbauer measurements on AgFeO₂ powder sample recorded at various temperatures including the points of both magnetic phase transitions. The ⁵⁷Fe Mössbauer spectra of AgFeO₂ measured in the paramagnetic range (T > T _N1) consist of one quadrupole doublet with rather high quadrupole splitting of Δ_300K = 0.66 ± 0.01 mm/s for Fe³⁺ ions. In order to predict the sign of electric field gradient (EFG) at ⁵⁷Fe nuclei, we calculated the lattice contribution to the electric field gradient (EFG) at ⁵⁷Fe nuclei, which emphasized the importance of the dipolar contributions, with resultant oxygen polarizabilities in the range of α _O = 0.83 ų, in agreement with the results obtained previously for other delafossite-like oxides. In the temperature range of T _N2 < T < T _N1, Mössbauer spectra gave clear evidence for the existence of a distribution of the hyperfine magnetic fields H _hf at ⁵⁷Fe nuclei. We present the results of a model fitting of the spectra based on an assumption of the cycloid magnetic structure of AgFeO₂ at T < T _N2. The obtained data were analysed in comparison with published data on Mössbauer studies of oxide multiferroics.     

Mössbauer study of cubic pyrochlores,Bi2−xYxFeSbO7

The solid solutions Bi_2?xY_xFeSbO₇ (x = 0,1,2) which are cubic pyrochlores of the type A₂B₂O₇ have been prepared for the first time and the lattice parameters determined. The ⁵⁷Fe Mössbauer spectra have been recorded both in the paramagnetic and magnetically ordered states. From the values of the Mössbauer parameters it is found that Fe ions are in the high spin trivalent state. The large value for the quadrupole splitting of these compounds is attributed to the highly distorted BO₆ octahedron in these compounds. The quadrupole splitting decreases with increase of Bi concentration and therefore, the BO₆ octahedron is found to have the lowest distortion for the composition Bi₂FeSbO₇. The magnetic transition temperature and the value of the magnetic hyperfine fields have been determined. The distribution of Fe³⁺ and Sb⁵⁺ ions in B sites gives rise to the distribution in magnetic hyperfine fields.     

Mise en évidence d'un échange électronique entre Fe2+ ET Fe3+ dans les oxydes rhomboédriques AFe2O4 par spectroscopie mossbauer DU57Fe

The ABB'O₄ rhomboedral oxides containing exclusively either Fe²⁺(InFeGe_0,5Zn_0,5O₄) or Fe³⁺(LuMg-FeO₄ and LuMnFeO₄) are investigated with Mössbauer spectroscopy, in their paramagnetic state.A similar study is made on two mixed oxides containing iron under its two oxidation states, with the $\text{Fe}{}^{\mathrm{2+}}\text{Fe}{}^{\mathrm{3+}}\text{= 2}$ and 1 (InFe_1,5Ga_0,5O₄ and InFe₂O₄) atomic ratio.Comparing the results, we have come to the conclusion that a fast electronic exchange between Fe²⁺ and Fe³⁺ takes place at room temperature. In this structure, point Fe²⁺ and Fe³⁺ are distributed on the same crystallographic site with the point symmetry C_3v. We show that neighbouring effects lower this local symmetry.     

Magnetic properties of the garnets Bi0·8Ca2χT2·2-2.χFe5-χVχ]O12

The behaviour of the magnetization, Curie temperature, Mössbauer spectra, and lattice parameter is studied in the garnet series Bi_0·8Ca_2.χT_2·2-2.χFe_5-χV_χ]O₁₂. The shape of magnetization vs temperature curves shows only a minor dependence on x. The hyperfine field at the octahedral ⁵⁷Fe nuclei at 5°K decreases linearly with x (12·5kOe per substituted V neighbour), while that at the tetrahedral ⁵⁷Fe nuclei is not affected. The dependence of the Curie temperatures and hyperfine fields on x is discussed in relation to the Fe-O-V-O-Fe exchange. The influence of Bi substitution is consistent with the idea of a geometric effect.     

A 57Fe and 119Sn Mössbauer study of BaFe4Sn2O11

The Mössbauer spectrum of BaFe₄Sn₂O₁₁ has been recorded for both ⁵⁷Fe and ¹¹⁹Sn isotopes at a variety of temperatures. In the paramagnetic state the ⁵⁷Fe spectra are interpreted in terms of three iron environments. Magnetic ordering begins at 77 K and is virtually complete by 4.2 K to give an average magnetic hyperfine field of 504 kG. The ¹¹⁹Sn spectra also reflect the magnetic ordering and a magnetic hyperfine field of 45 kG is transferred to the tin nuclei.     

Low-temperature Mössbauer studies of FeNb2O6

Fe⁵⁷ Mössbauer spectra of FeNb₂O₆ were obtained from 15.0K down to 1.9 K. The isomer shift, 1.42±0.01 mm sec^?1 relative to Cr, was found to be temperature independent, whereas the magnitude of the quadrupole splitting was observed to decrease slightly with temperature. The quadrupole splitting and the hyperfine field at 1.9 K are -2.41±0.01 mm sec^?1 and 34.6±0.3 kOe respectively. The directions of the hyperfine fields experienced by the Fe nuclei are in the a-c plane symmetrically displaced with respect to the crystallographic axes.     

Mössbauer effect in LaFe12O19

Mössbauer spectra of ⁵⁷Fe in LaFe₁₂O₁₉ show that the substitution of La³⁺ for Ba²⁺ or Sr²⁺ in XFe₁₂O₁₉ is associated with a valency change of Fe³⁺ to Fe²⁺ at the 2a or 4f₂ site. Temperature dependences of the hyperfine fields at the various sublattices are given.     

Mössbauer study of the modified pyrochlores CsMFeF6 (M = Mn,Ni)

⁵⁷Fe Mössbauer spectra of the modified pyrochlores CsMFeF₆ (M = Mn, Ni) were obtained between 1.5 K and room temperature. The spectra for single crystal and powder absorbers are very similar, and demonstrate the randomness associated with the iron sites. Nevertheless, the presence of two distinct iron sites, recently reported by Varret and Courbion for powder samples, is confirmed. Both CsMnFeF₆ and CsNiFeF₆ are antiferromagnets with Néel temperatures, T_N, of 25 and 5.2 K, respectively. The hyperfine fields lie on the Brillouin function with $\text{S =}\text{5}\text{2}$. The hyperfine parameters show that the iron ions are ferric in the high-spin state.     

Mössbauer studies of spatial spin-modulated structure and hyperfine interactions in multiferroic Bi<Superscript>57</Superscript>Fe<Subscript>0.10</Subscript>Fe<Subscript>0.85</Subscript>Cr<Subscript>0.05</Subscript>O<Subscript>3</Subscript>

Results of Mössbauer investigations on ⁵⁷Fe nuclei in multiferroic material Bi⁵⁷Fe_0.10Fe_0.85Cr_0.05O₃ in the temperature range from 5.2 to 300 K are presented. Bulk rhombohedral samples were obtained by solidstate synthesis at high pressure. Mössbauer spectra were analyzed using the model of spatial incommensurate spin-modulated structure of the cycloidal type. Information on the influence of substituting Cr cations for Fe cations on hyperfine spectral parameters was obtained: the shift and quadrupolar shift of a Mössbauer line, and isotropic and anisotropic contributions into the hyperfine magnetic field. The anharmonicity parameter m of the spatial spin-modulated structure increases almost 1.7 times at 5.2 K when BiFeO₃ is doped with chromium. The data on m were used for calculation of the uniaxial magnetic anisotropy constants and their temperature dependences for pure and chromium-doped BiFeO₃.     

Mössbauer spectroscopic properties of tin-doped iron oxides

The ⁵⁷Fe Mössbauer spectra recorded in situ from tin-doped Fe₃O₄ at elevated temperature in vacuo shows the Curie temperature to decrease with increasing concentrations of the dopant. Thermal treatment under oxidising conditions results in the initial formation of tin-doped γ-Fe₂O₃ which subsequently undergoes a phase transformation to tin-doped α-Fe₂O₃. ⁵⁷Fe Mössbauer spectroscopy at elevated temperatures shows the Néel temperature for tin-doped γ-Fe₂O₃ to be lower than that of pure γ-Fe₂O₃. The ¹¹⁹Sn Mössbauer spectra recorded from all the tin-doped iron oxides show the presence of a hyperfine magnetic field at the Sn⁴⁺ site which is more complex in the spectra recorded from tin-doped γ-Fe₂O₃ and α-Fe₂O₃.     

Mössbauer and magnetic studies of BaVS3 and V5S8 doped with 57Fe

Iron can be easily introduced in BaVS₃ and V₅S₈. It is located at the vanadium sites and has been used as a probe to analyse by Mössbauer effect the magnetic properties of its surrounding matrix. The electronic state of iron in this matrix has also been studied. It was found that in BaVS₃, the iron is in a low spin Fe³⁺ configuration $\text{(S =}\text{1}\text{2}\text{)}$. In V₅S₈ at 4.2 K, the iron is in low spin Fe²⁺ configuration (S = 0). The rapid decrease of quadrupole splitting observed between 50 and 200 K is attributed to a thermally activated change in electronic structure. The high temperature configuration (above 200 K) seems to be neither pure low spin Fe³⁺ nor high spin Fe²⁺, but a mixture of configurations fluctuating at a rate which is faster than the characteristic time of Mössbauer measurements.     

Mössbauer spectroscopy on57Fe in highT c superconductor Bi2Sr2Ca1Cu2O y

Mössbauer measurements were performed on polycrystalline⁵⁷Fe: Bi₂Sr₂Ca₁Cu₂O _y , super-conductor in the temperature range of 77–296 K. The samples were obtained in a solid phase synthesis using 0.01, 0.03, 0.1 and 0.5 mol fractions of α-Fe₂O₃ (96% enriched in⁵⁷Fe). A prevailing quadrupole doublet practically independent of temperature and iron concentration characterizes the obtained Mössbauer spectra. The corresponding hyperfine parameters suggest the presence of high spin Fe¹¹¹ ions in a strongly distorted octahedral symmetry which indicates a probable copper substitution by iron in the system.