Mössbauer study on iron-polygalacturonate coordination compounds

⁵⁷Fe Mössbauer spectroscopy was used to determine the oxidation state and microenvironments of iron in the Fe-polygalacturonate compound prepared by a novel method from pectin. ICP analysis was applied to study the iron content of the coordination compounds. It was found that there are two ferrous and one ferric microenvironments in the compound. In the iron- polygalacturonate compound the ferrous forms occur dominantly. A model for the bonding of Fe in the polygalacturonate chains is proposed.     

High-field Mössbauer spectroscopy on dinuclear iron(II) spin crossover complexes

The dinuclear complex [{Fe(L-N₄Me₂)}₂(BzImCOO)](ClO₄)₂*0.5(CH₃)₂CO has been investigated by Mössbauer spectroscopy carried out in the temperature range from T = 5 K up to T = 190 K with externally applied magnetic fields of up to B = 5 T. By means of a consistent simulation of all experimental data sets within the Spin Hamiltonian formalism, the zero-field splitting and the rhombicity parameter of the ferrous high-spin site could be determined to be D?= 7.2 ± 0.5 cm^???1 and E/D?= 0.1 ± 0.02. The sign of the quadrupole splitting is positive which indicates that the ferrous high-spin site of the dinuclear complex [{Fe(L-N₄Me₂)}₂(BzImCOO)]-(ClO₄)₂*0.5(CH₃)₂CO has an electronic ground state with the d _xy orbital twofold occupied.     

Mössbauer study on characterization of Co[Fe(CN)5NH3 \cdot x H2O

The electronic states of Fe atoms in Co[Fe(CN)₅NH₃ H₂O were studied by means of ⁵⁷Fe Mössbauer spectroscopy. The Mössbauer spectra of Co[Fe(CN)₅NH₃ 6H₂O show the coexistence of mixed valences for the Fe atoms and a magnetic relaxation at 4 K. When water molecules were removed, electron transfer from Co to Fe occurred.     

Mössbauer study on Fe0.068Ni0.932Cl2 with competing spin anisotropies

Mössbauer measurements on Fe_0.068Ni_0.932Cl₂ were done at temperatures between 55K and 4.2K. We have found that below T_N-50K an observed spectrum is composed of two kinds of spectra and that the composition ratio changes gradually with temperature. The average angle of Fe²⁺ spins, \(\overline {\theta _{Fe} } \) , with the c-axis is smaller than \(\overline {\theta _c } \) by ?15° at each temperature below T_N, where \(\overline {\theta _c } \) is the average angle of total spins with the c-axis in this system obtained from the neutron scattering measurements. This is reasonably understood if we take into account that Fe²⁺ spins have the strong uniaxial anisotropy along the c-axis. We discuss the coexistence of the two kinds of spectra by considering the exchange energy of Fe²⁺ spins and the local magnetic anisotropy.     

Pressure-induced coordination crossover in magnetite,a high pressure Mössbauer study

Temperature-dependent ⁵⁷Fe Mössbauer spectroscopy to 40 GPa shows that Fe₃O₄ magnetite undergoes a coordination crossover (CC) whereby charge-density is shifted from octahedral to tetrahedral sites and the spinel structure thus changes from inverse to normal with increasing pressure and decreasing temperature. A precursor to the CC is a d-charge decoupling within the octahedral sites at the inverse spinel phase. The CC-transition takes place almost exactly at the Verwey transition temperature (T_V=122 K) at ambient pressure. While T_V decreases with pressure, the CC-transition temperature increases with pressure, reaching 350 K at 10 GPa. The d electron localization mechanism proposed by Verwey and later by Mott for T<T_V is shown to be unrelated to the actual mechanism of the metal–insulator transition attributed to the Verwey transition. It is proposed that a first-order phase transition taking place at ∼T_V at ambient pressure opens a small gap within the oxygen p-band, resulting in the observed insulating state at T>T_V.     

57Fe Mössbauer spectroscopic study of nanostructured zinc ferrite

Nanosize zinc ferrite particles, prepared by nitrate method, were investigated by XRD, TEM, ⁵⁷Fe Mössbauer spectroscopy and VSM. The average particle size in this system varies from 10 to 62 nm as the sintering temperature increases from 300°C to 1,000°C. The lattice parameters in this system are almost constant at a value of ～8.41 Å. The Mössbauer spectra of all the sintered samples show a single doublet. The Mössbauer hyperfine parameters show little change with the change of sintering temperature. The doublets are ascribed to the presence of superparamagnetism in this system, which is also corroborated by the VSM measurements.     

A Mössbauer spectroscopic study of 3d magnetism of R2Fe14B

Guided by the occupancies and iron magnetic moments μ³, ⁵⁷Fe Mössbauer parameters of Y₂Fe₁₄B at 250K, and in turn for other temperatures, of the sublattices of iron were deduced. Plots of μ(T) in reduced coordinates, through the established correlation between hyperfine field Hn and μ, show that the corresponding state of different iron sites is different and all experimental points fall below Brillouin function. The relation between exchange integral deviation parameter Δ and standard deviation of Fe-Fe interatomic distances S is linear, indicating electrostatic nature of exchange interactions between spins in neighboring atoms. It is inclined to the view that fluctuations of exchange integral is responsible for low T_c of R₂Fe₁₄B.     

Magnetic and Mössbauer studies of cyanide-bridged bimetallic assembly [Mn(cyclam)][Fe(CN)6]·3H2O

Cyanide-bridged bimetallic assembly [Mn(cyclam)][Fe(CN)₆]·3H₂O (cyclam=1,4,8,11-tetraazacyclotetradecane) was synthesized from the reaction of trans-[MnCl₂(cyclam)]Cl with K₃Fe(CN)₆. A linear chain structure consisting of alternating [Mn(cyclam)]³⁺ and [Fe(CN)₆]³⁻ units was indicated by the IR and Mössbauer spectra. The variable-temperature magnetization and Mössbauer measurements revealed that this complex exhibited a long-range ordering below 6.8 K. The magnetic behavior of the complex was based on intrachain ferromagnetic and interchain antiferromagnetic interactions.     

Study on the spin crossover transition and glass transition for Fe(II) complex film, [Fe(II)(H-triazole) 3 ]@Nafion, by means of M?ssbauer spectroscopy

[Fe(II)(H-trz)₃]@Nafion (trz = triazole) is a transparent spin crossover complex film, where the spin crossover transition between the low-spin (S = 0) and the high-spin (S = 2) states takes place between 225?K and 300?K. In this film, two doublets corresponding to the low-spin and high-spin states were observed in the ⁵⁷Fe M?ssbauer spectra, reflecting the spin crossover transition. From the analysis of ⁵⁷Fe M?ssbauer spectra, the Debye temperatures of the low-spin and high-spin sites were estimated at 185?K and 176?K, respectively, in the temperature range between 10?K and 150?K. In this film, the total intensity of the M?ssbauer spectra corresponding to the low-spin and high-spin sites drastically decreases above 200?K, reflecting the glass transition of Nafion, where the lattice vibration of [Fe(H-trz)₃] $_{\rm n}^{\,\,\rm 2n+}$ is softened just as in solution due to micro-Brown motion of the segment of Nafion polymer membrane.     

Iron nano-clusters in ytterbium films: a 57Fe Mössbauer spectroscopic study

We have performed a Mössbauer study on iron clusters that are formed in ytterbium films prepared by vapor co-deposition onto kapton substrates kept at room temperature. The film thicknesses were chosen in a range between 2.5 and 2.8 $\upmu$ m. XRD of the films reveals a mixture of fcc- and hcp-like ytterbium. Iron concentrations were between 0.3 and 5 at %. All samples reveal hyperfine spectra attributed to only two types of iron clusters with well defined hyperfine parameters. The clusters are supposed to be formed at boundaries of hcp- and fcc-like grains. In addition there is found a small contribution from monomeric iron. Spectra taken at 4.2 K reveal a complex distribution of magnetic hyperfine fields. The dynamic origin of the spectral shape is supported by susceptibility data revealing spin-freezing at temperatures below ca. 10 K. This proves that the iron clusters have sizes on the order of nm.     

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 Y2Fe17N x (x < 3) nitrides

⁵⁷Fe Mössbauer spectra of Y₂Fe₁₇N_x nitrides were measured. The hyperfine field (H _hf) and the average isomer shift for Y₂Fe₁₇ increase obviously after nitrogenation. Forx1.1, however, the averageH _hf varies only slightly, while the increase ofH _hfat each iron site is somewhat different and more pronounced at 4f dumbbell sites than at the other sites when the nitrogen concentration is increased. This means that the influence of the nitrogen atoms on the local magnetic properties of the iron atoms depends sensitively on the configuration of the nearest-neighbor atoms around the iron atoms. The results are compared with the⁸⁹Y NMR spectra of Y₂Fe₁₇N _x .This project was supported by the National Natural Science Foundation and the State Key Magnetism Laboratory of China.     

57Fe Mössbauer study of Lu2Fe3Si5 iron silicide superconductor

With the advent of Fe–As based superconductivity it has become important to study how superconductivity manifests itself in details of ⁵⁷Fe Mössbauer spectroscopy of conventional, Fe-bearing superconductors. To this end, the iron-based superconductor Lu₂Fe₃Si₅ has been studied by ⁵⁷Fe Mössbauer spectroscopy over the temperature range from 4.4 K to room temperature with particular attention to the region close to the superconducting transition temperature (T_c=6.1 K). Consistent with the two crystallographic sites for Fe in this structure, the observed spectra appear to have a pattern consisting of two doublets over the whole temperature range. The value of Debye temperature was estimated from temperature dependence of the isomer shift and the total spectral area and compared with the specific heat capacity data. Neither abnormal behavior of the hyperfine parameters at or near T_c, nor phonon softening were observed.     

Mössbauer spectroscopic study of FeII-doped sulphonated poly(ether-urethane)—styrene-acrylate copolymer

Thermoplastic linear ionomer based on sulphonated poly(ether-urethane)—styrene-acrylate copolymer, doped with natural Fe^2?+?, was studied by Mössbauer spectroscopy at T?= 78 and 290 K to monitor the chemical state of Fe species. The Fe^2?+? added to aqueous suspension of the system was only partly oxidised in the course of polymer film preparation and drying in air. The oxidised part comprised a magnetic phase (~19 % of total Fe both at T?= 78 and 298 K) and a quadrupole doublet (~40 %), while Fe^II (over 40 %) stabilised in two types of microenvironments.     

Mössbauer study of the ternary system (Fe1−xVx)3 Ge

Three crystallographically different structures of (Fe_1–xV_x)₃ Ge have been studied by⁵⁷Fe Mössbauer spectroscopy. The hexagonal phase, stable for low values ofx, is ferromagnetic with the spins parallel to thec-axis above a critical temperature, where a spin flip to thec-plane takes place. A V/Fe substitution in the near surrounding of an iron atom leads to a decrease in the isomer shift of –0.02 mm/s and an estimated reduction in the magnetic moment of 0.31 _B from 2.07 _B. A result for the intermediate cubic closed packed structure is that V populates only one type of metal sites. Furthermore, from similarities with-Fe the average value of the change in isomer shift is found to be +0.075 mm/s and +0.02 mm/s per Ge/Fe substitution in the 1nn and 2nn shells, respectively. The spin polarization effect on the magnetic hyperfine field for iron is –8.6%, –0.4%, and –0.6% per Ge/Fe (1nn), Ge/Fe (2nn) and V/Fe (3nn) substitutions, respectively. The simple cubic compound (Fe_0.7V_0.3)₃ Ge is non-magnetic down to at least 5 K. Here a decrease in the isomer shift of –0.05 mm/s is found for a V/Fe (1nn) substitution.On leave from the Department of Nuclear Physics, University of Madras, Madras, India.On leave from the Physics Department, Punjabi University, Patiala, India.     

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.     

A57Fe Mössbauer study of Nd(Fe0.5Co0.5)9Si2

A⁵⁷Fe Mössbauer study of Nd(Fe_0.5Co_0.5)₉Si₂ has been carried out over the temperature range 4.2–295 K. The analysis of the Mössbauer spectra, combined with X-ray diffraction on a magnetically aligned powder sample, shows that the easy-magnetization direction lies in the basal plane of this tetragonal BaCd₁₁ structure at 295 K, but is canted at an angle of 29(5) above the basal plane at 4.2 K. AC susceptibility measurements performed in the temperature range 77–295 K reveal a peak spanning the range 87–106 K, with the maximum occurring at 96 K. From these data, we conclude that there is a spin-reorientation from basal c-plane to a canted magnetic structure in this compound, with an onset at 96 K as the temperature decreases.     

Octahedral cation partitioning in Mg,Fe2+-olivine. Mössbauer spectroscopic study of synthetic (Mg0.5 Fe2+ 0.5)2SiO4 (Fa50)

The high-temperature partitioning of Fe²⁺ and Mg between the two non-equivalent octahedral M1 and M2 sites in synthetic olivine (Fa₅₀) was studied by Mössbauer spectroscopy. Powder samples have been equilibrated in annealing experiments performed under reducing oxygen fugacity at temperatures between 500 and 800°C followed by rapid quenching in order to prevent redistribution of cations. M-site ordering with Fe²⁺ preferring M1, Mg preferring M2 sites increases continuously with rising equilibrium temperature. K _D values increase from 1.21 at 500°C to 1.48 at 750°C. The results are consistent with both room temperature as well as in situ high temperature single crystal X-ray diffraction experiments of Heinemann et al. [8, 9].     

Mössbauer spectroscopic studies of spin crossover in tris(N, N′-dialkyldithiocarbamato) iron (III) complexes: effect of alkyl substituents

Spin crossover behavior in tris(N,N′-dialkyldithiocarbamato) iron(III) complexes with varying alkyl groups has been studied by variable temperature magnetic moment and Mössbauer spectral studies. All the complexes may be divided into three broad groups; high spin (μ _eff > 4.8 BM), intermediate spin (μ _eff?=?3.5???4.6 BM) and low spin (μ _eff?< 3.2 B.M). Room temperature (RT) Mössbauer spectra exhibit an asymmetric doublet resolved into two doublets corresponding to high and low spin states. Estimated % contributions of HS and LS states and calculated μ _eff were comparable with the experimentally determined values. It has been shown that some complexes undergo spin crossover, ⁶A₁g→²T₂g whereas others exhibit spin transitions ⁶A₁g →⁴T₁g or ⁴T₁g → ²T₂g. IR spectra show characteristic ν _(Fe???S) bands in the region 208–285 (HS) and 311–380 cm^???1 (LS). Nature of alkyl groups affects the spin state.