57Fe Mössbauer spectroscopy on disordered crystalline media with Ca-gallogermanate type structure. I. In the paramagnetic range

Polycrystalline strontium iron germanates of the type Sr_3–y Ln _y Fe_2+y Ge_4–y O₁₄(Ln=La, Nd;y=0, 1) were investigated by⁵⁷Fe Mössbauer spectroscopy in the temperature range 4.2–300 K. The crystal chemistry and the distribution of Fe³⁺ ions in the structure, as well as the crystallographic inequivalence of the oxygen polyhedra occupied by iron, were studied over the whole paramagnetic temperature region. A correlation of the experimental data with a local environment computation is given.     

X-ray and Mössbauer study of rapidly solidified Ce20Fe80 ribbons; effect of the quenching rate

Ce₂₀Fe₈₀ ribbons have been produced by planar flow casting under an He atmosphere at linear wheel velocities between 19 and 29 m s^–1. Analysis of ribbons by X-ray diffraction and⁵⁷Fe Mössbauer spectrometry in the temperature range 77–300 K shows that the ribbons are crystallized. For higher velocities, the ribbon is constituted of the two equilibrium phases CeFe₂ and Ce₂Fe₁₇, but, for lower velocities, there appears a third iron metallic phase, which can be explained by the quenching rate of the melt. A coherent hyperfine parameter set was deduced from fitting Mössbauer spectra in the whole temperature range.     

Investigation of spin structure in fcc Fe-Ni-Mn

⁵⁷Fe Mössbauer spectra of Invar type (Fe_.65Ni_.35)_1–xMn_x alloys (O相似文献   

Mössbauer study of Na0.82Co0.99Fe0.01O2

We studied by Mössbauer spectroscopy the Na_0.82CoO₂ compound using 1% ⁵⁷Fe as a local probe which substitutes for the Co ions. Mössbauer spectra at T=300 K revealed two sites which correspond to Fe³⁺ and Fe⁴⁺. The existence of two distinct values of the quadrupole splitting instead of a continuous distribution should be related with the charge ordering of Co⁺³, Co⁺⁴ ions and ion ordering of Na(1) and Na(2). Below T=10 K part of the spectrum area, corresponding to Fe⁴⁺ and all of Fe³⁺, displays broad magnetically split spectra arising either from short-range magnetic correlations or from slow electronic spin relaxation.     

Structural and magnetic properties of rapidly solidified (Ce0.2Fe0.8)1-x Al x ribbons determined by X-ray diffraction and Mössbauer spectrometry

(Ce_0.2Fe_0.8)_1-x Al _x (0 x 0.9) ribbons have been prepared by planar flow casting under an He atmosphere with a linear velocity of 29 m s^-1. Analyses of the ribbons by X-ray diffraction and⁵⁷Fe Mössbauer spectrometry in the temperature range 4–300 K show that all the ribbons are crystalline. With increasingx, the observed phases are Ce(Fe, Al)₂, Ce₂(Fe, Al)₁₇, CeFe_4+y,Al_8-y and the single fcc aluminium phase. For the different phases, the line intensities of the Mössbauer spectra agree with previous results on the preferential substitution sites for aluminium. A coherent hyperfine parameters set was deduced from fitting spectra in the temperature range 4–300 K.     

Study of [Fe(pyim)3] complexes: dynamic spin equilibrium on encapsulation in zeolite Y

Tris complex of Fe^II2(2′-pyridyl)imidazole has been encapsulated in the supercages of zeolite Y and characterized by using powder XRD, FTIR, Mössbauer spectroscopy, variable temperature magnetization and MAS NMR techniques and results have been compared with those obtained for this complex with ClO₄⁻ and SO₄²⁻ as anions. At room temperature, the [Fe(pyim)₃](ClO₄)₂ complex exhibited low spin state, while [Fe^II(pyim)₃]SO₄ exhibited the existence of both low and high spin states. The encapsulated [Fe^II(pyim)₃]²⁺ complex exhibited a broad quadrupole doublet characterized by isomer shift, δ=+0.55 mm/s and quadrupole splitting ΔE_q=1.26 mm/s. The magnetization measurements carried out for the encapsulated [Fe^II(pyim)₃]²⁺ complex showed a systematic decrease in its values with decreasing temperature down to 75 K with no indication of thermal hysteresis effects. These results suggest the existence of a dynamic spin state equilibrium between the high and low spin states for the encapsulated [Fe^II(pyim)₃]²⁺ complex with time constant comparable to the characteristic Mössbauer time scale of ⁵⁷Fe nuclei.     

A Mössbauer effect study of the bonding in some organoiron-copper clusters

The Mössbauer effect spectra of structurally characterized molecular metal clusters provide a valuable reference point for the identification of surface generated species important in chemisorption and catalysis. The resulting hyperfine parameters may also aid structural elucidation and provide insight into the electronic environment of the individual iron sites. We have studied in detail the clusters Na₂Cu₆Fe₄(CO)₁₆, Na₃Cu₅Fe₄(CO)₁₆, and Na₃Cu₃Fe₃(CO)₁₂, and several related compounds. The results indicate that the Mössbauer effect isomer shifts at 78K, which vary from –0.123 to –0.035mm/s, are very sensitive to the bonding in the molecular cluster.     

Mössbauer,X-ray diffraction and AC susceptibility studies on nanoparticles of zinc substituted magnesium ferrite

Nanoparticles of zinc substituted Mg-ferrite with compositions Mg_(1-x)Zn _x Fe₂O₄ (x = 0.15, 0.30 and 0.50) having particle sizes in the range 6.4 nm to 21.4 nm prepared by the co-precipitation method were characterized by ⁵⁷Fe Mössbauer spectroscopy, X-ray diffratometry and AC magnetic susceptibility measurements. Mössbauer measurements at room temperature and down to 20 K clearly indicate presence of superparamagnetic particles in all the samples. AC magnetic susceptibility data show lowering of blocking temperature with decrease of particle size. Superparamagnetic relaxation was observed for larger particle size in samples with higher Zn content, which is attributed to the weakening of A-B exchange interaction in ferrite lattice due to replacement of Fe^{3 +} in tetrahedral site by Zn^{2 +} ions.Received: 16 April 2004, Published online: 23 July 2004PACS: 75.50.Tt Fine-particle systems; nanocrystalline materials - 76.80. + y Mössbauer effect; other gamma-ray spectroscopy - 75.30.Cr Saturation moments and magnetic susceptibilitiesS. Das: Present address: Department of Physics, Jadavpur University, Kolkata - 700032, India     

Fe57 Mössbauer study in cobalt substituted magnetite

The Mössbauer effect has been studied in the mixed ferrites Co _x Fe_3–x O₄ (forx=0.8, 0.9 and 1) with the spinel structure in the temperature range between 78 and 380 K. The composition withx=1, showed an expected Zeeman spectrum with two overlapping magnetic hyperfine patterns related to the Fe³⁺ ions in tetrahedral and octahedral sites. While for samples withx=0.8 and 0.9 the Mössbauer spectrum for each compound was successfully analysed into three different patterns corresponding to the ferric ions placed at the tetrahedral and octahedral sites and ferrous ions at the octahedral sites, indicating no electron transfer between Fe³⁺ and Fe²⁺, where the quantity of cobalt is sufficiently large to be located at the six nearest neighbours to ferrous ions. The Mössbauer effect parameters were calculated for these observed sites and their variation with temperature reported. The reduced hyperfine magnetic fields of the Fe³⁺ (B) ions were found to follow the Brillouin curve forS=5/2 and one third power law. The magnetic ordering temperature was determined to be 815 K and the possible magnetic interactions were discussed.     

Mössbauer spectroscopy as a probe of magnetic states in La0.5Ca0.5FeO3−δ perovskite

Charge disproportionation in La_0.5Ca_0.5FeO_3−δ perovskite has been detected by zero-field Mössbauer spectra from 20 K to room temperature. On the basis of the parameters of center shifts and hyperfine fields, Mössbauer spectra identified that the iron ionic states are Fe³⁺ and Fe⁵⁺ below 150 K, Fe³⁺, Fe⁴⁺ and Fe⁵⁺ in the intermediate temperature region, as well as Fe³⁺ and Fe⁴⁺ above 220 K. At low temperatures, the system exhibits a cluster-glass-like state resulting from competition between antiferromagnetic interaction of Fe³⁺–Fe³⁺ and ferromagnetic interaction of Fe³⁺–Fe⁵⁺.     

Investigation of Fe structural environments in “leucite”-type framework silicates using a combination of Mössbauer and X-ray absorption spectroscopies

Synthetic iron-containing leucite-type phases have been studied using⁵⁷Fe Mössbauer spectroscopy in combination with X-ray absorption spectroscopy (XAFS and XANES). The Mössbauer and XAS data confirm that both Fe²⁺ and Fe³⁺ occupy tetrahedrally coordinated framework sites in the synthetic phases. In addition, information on Fe²⁺/Fe³⁺ ratios, cation site occupancies and first shell bond lengths has also been obtained.     

Mössbauer and magnetic studies of orthorhombic FeSiO3

Magnetic properties of orthoferrosilite FeSiO₃ have been examined using susceptibility, magnetization measurements and Mössbauer spectroscopy. From magnetic and Mössbauer measurements, one obtains close values of the magnetic ordering temperature, T_N=39±1 K and T_N=41±1 K, respectively. The magnetic order is characterized by strong ferromagnetic coupling of Fe²⁺ moments within the ribbons and a weak antiferromagnetic coupling of the moments between adjacent ribbons. The 4.2 K Mössbauer spectra can be fitted with two different hyperfine magnetic fields H_hf=68 kOe and H_hf=314 kOe which can be assigned to Fe²⁺ in the octahedrally coordinated M1 and M2 sites, respectively, of the FeSiO₃ structure.     

Mössbauer study of magnetic order in RBa2Fe3O8

Complete replacement of copper by iron in RBa₂Cu₃O₇ leads to RBa₂Fe₃O₈ (R=Y, rare earth). Mössbauer spectroscopy measurements of⁵⁷Fe and¹⁵¹Eu in RBa₂Fe₃O₈ (R=Y, Eu, Ho, Er) at temperatures 4.2–800 K have been performed. Some of the spectra reveal two inequivalent iron sites, probably corresponding to iron in the Fe(2) site (fivefold oxygen coordination) and in the Fe(1) site (octahedral oxygen coordination). In all compounds the iron moments order antiferromagnetically at the same Néel temperatureT _N720 K. The¹⁵¹Eu Mössbauer spectra of EuBa₂Fe₃O₈ show that the Eu ion is trivalent and exposed to a small exchange field from the iron sublattices.     

Molecular magnetism of a linear Fe(III)-Mn(II)-Fe(III) complex. Influence of long-range exchange interaction

The magnetic properties of [L-Fe(III)-dmg₃Mn(II)-Fe(III)-L] (ClO₄)₂ have been characterized by magnetic susceptibility, EPR, and Mössbauer studies. L represents 1,4,7-trimethyl-, 1,4,7-triazacyclononane and dmg represents dimethylglyoxime. X-ray diffraction measurements yield that the arrangement of the three metal centers is strictly linear with atomic distancesd _Fe-Mn=0.35 nm andd _Fe-Fe=0.7 nm. Magnetic susceptibility measurements (3–295 K) were analyzed in the framework of the spin-Hamiltonian formalism considering Heisenberg exchange and Zeeman interaction:=J _Fe-Mn(S _Fe1+S _Fe2)S _Mn +J _Fe-Fe(S _Fe1 S _Fe2) +g_B S _total B. The spinsS _Fe1=S _Fe2 =S _Mn=5/2 of the complex are antiferromagnetically coupled, yielding a total spin ofS _total=5/2 with exchange coupling constantsF _Fe-Mn=13.4 cm^–1 andJ _Fe-Fe= 4.5 cm^–1. Magnetically split Mössbauer spectra were recorded at 1.5 K under various applied fields (20 mT, 170 mT, 4T). The spin-Hamiltonian analysis of these spectra yields isotropic magnetic hyperfine coupling withA _total/(g _{N N})=–18.5 T. The corresponding local componentA _Fe is related toA _total via spin-projection:A _total=(6/7)A_Fe. The resultingA _Fe/(g _NN)=–21.6 T is in agreement with standard values of ferric high-spin complexes. Spin-Hamiltonian parameters as obtained from Mössbauer studies and exchange coupling constants as derived from susceptibility measurements are corroborated by temperature-dependent EPR studies.     

Mössbauer and optical spectrometry of selected schörl-dravite tourmalines

Spectrometric studies were carried out on samples of tourmaline (schörl-dravite series) from geological environments where first-phase-formed tourmaline underwent influence of geochemically different fluids. Samples are from a differentiated magmatic complex of Trento-Alto Adige, Italy, and from hydrothermal gold and silver deposits of the Humboldt Range, Nevada, USA. Chemical data were obtained from electron microprobes. The results of Mössbauer measurements suggest three to five doublets. Fe occurs in two valence states. The Z-site, usually fulfilled with Al³⁺ and Fe³⁺, is assigned only to Al³⁺ and Fe²⁺. This location was found in nearly all samples studied. In the Y-site Fe²⁺ and Fe³⁺ are obviously present. Isomer shifts with intermediate values can be assumed to be related to intervalence charge transfer (IVCT). Optical spectroscopy reveals absorption bands at 9 000 and 14000 cm^–1, which are assigned to a charge transfer between Fe²⁺ and Fe³⁺, the 23 000 cm^–1 absorption band is supposed to be due to Fe²⁺ Ti⁴⁺ charge transfer. The occupation of the Z-site only by Fe²⁺ and the coexistence of divalent and trivalent Fe in the Y-site could be explained by selective oxidation in Y-site through a late process.     

Quadrupole Splitting Distributions in Purpurite and Related Minerals

The quadrupole splitting distributions (QSDs) from the Mössbauer spectra of triphylite, ferrisicklerite and purpurite at 298 K and 80 K were obtained by the use of the Voigt-based quadrupole splitting distribution (QSD) method for the first time. QSDs of Fe²⁺ and Fe³⁺ are attributed to Fe²⁺ and Fe³⁺ at the corresponding octahedrally coordinated sites in the crystal structures of the three phosphate minerals. The influence on the distortion of the M2 site by different next-nearest neighbor (NNN) configurations was discussed based on the Jahn–Teller effect in purpurite, and the authors propose two M2 subsites with different distortions in purpurite. Two QSDs of Fe³⁺ in the Mössbauer spectra of purpurite are tentatively assigned to Fe³⁺ at the two M2 subsites, and next-nearest neighbor (NNN) effects were used to interpret the Mössbauer spectra of purpurite.     

Mössbauer studies of YBa2(Cu1−x Fe x )3O7−d annealed in an inert atmosphere

YBa₂(Cu_1–x Fe _x )₃O_7–d annealed in an Ar atmosphere, then reoxygenated at various temperatures, has been studied by Mössbauer spectroscopy at 300 K and low temperature with and without an applied field of 5.5 T. The results are interpreted as being due to Fe clustering remaining in the chains rather than a significant transfer to the planes.     

Magnetic ordering in Fe-doped Gd2BaCuO5

The structural and magnetic properties of iron-doped Gd₂BaCuO₅ have been studied by X-ray diffractometry, Mössbauer spectroscopy and susceptibility measurements. Mössbauer data on Gd₂BaCu_0.8Fe_0.2O₅ show that at room temperature Fe is not magnetically ordered, displaying hyperfine parameters similar to those generally assigned to Fe at Cu(2) sites in the GdBa₂(Cu_1–x Fe _x )₃O₇ superconductor. Susceptibility measurements demonstrate that Gd₂BaCu_1–x Fe _x O₅ behaves like a three-dimensional antiferromagnet withT _N=11.9±0.1 K, independent ofx. The effective magnetic moment calculated within a mean field approximation is consistent with an ordering of the Gd sublattice.     

Mössbauer study and magnetic moments of Fe90−xCoxZr10 and Fe90−xNixZr10 amorphous alloys

The⁵⁷Fe Mössbauer spectroscopy of amorphous Fe_90–xCo_xZr₁₀ and Fe_90–xNi_xZr₁₀ provided strong evidence for the unusual large enhancement of the Fe magnetic moment in these alloys.