Fast relaxation of polycrystalline Fe(III) complexes studied by Mössbauer spectroscopy

Mössbauer spectra of polycrystalline samples of Fe(Ox)₃, Fe(BPHA)₃ and K₃[Fe(malonate)₃] · 3H₂O exhibit fast relaxation patterns in the temperature range 4.2–300 K. The magnetic hyperfine splitting has nearly completely collapsed due to rapid electronic spin-spin relaxation of the Fe ions. We use a static Hamiltonian and describe the spin-spin interaction by an effective field Hamiltonian . From this the relaxation supermatrix and the Mössbauer spectra are calculated. The random texture of the samples is taken into account by averaging the radiation dipole operators over the whole sphere. Least-squares fits of the spectra for longitudinal, isotropic and transverse spin relaxation are presented. From the fits the temperature dependence of the relaxation is obtained. We conclude that in these materials the iron is present as high-spin Fe(III) and that the crystal field splitting constantD is greater than zero. The sign ofV _zz is found to be positive.     

Mössbauer spectroscopy on57Fe: NaCl crystals

Mössbauer absorbtion spectra of⁵⁷Fe-doped NaCl crystal were measured and correlated with an adequate electric field gradient computation to describe the dipolar complexes occuring at the decay of Suzuki-phase under thermal treatment and X-ray irradiation. An electrostatic potential of the type was taken into account in the evaluation of EFG tensor.     

In situ high-pressure study of LiNbO3-type FeTiO3: X-ray diffraction and Mössbauer spectroscopy

The structure of LiNbO₃-type FeTiO₃ and the oxidation state of Fe have been investigated using X-ray diffraction and Mössbauer spectroscopy in the diamond anvil cell up to 18 GPa at room temperature. A structural phase transition is observed at 15.7 GPa from LiNbO₃-type to perovskite-type, accompanied by a volume collapse of 1.5%. LiNbO₃-type FeTiO₃, which is shown to contain only ferrous iron up to this pressure, and no charge transfer is observed. In addition to the c/a axial ratio that has been used to distinguish between ilmenite and LiNbO₃-type FeTiO₃, the hyperfine parameters (isomer shift and quadrupole splitting) provide an efficient way to discriminate between these two phases.     

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 of the new iron oxide Fe3B7O13(OH)

In order to investigate the electronic state, the local structure, and the magnetic structure of a new ion oxide Fe₃B₇O₁₃(OH), we have applied ⁵⁷Fe Mössbauer spectroscopy. The room-temperature values of isomer shift and quadrupole splitting are 1.16 mm/s and 3.21 mm/s, respectively, which indicate that the Fe ions are in high spin Fe^2?+? state. The spectrum at 4.2 K is composed of a well-resolved hyperfine sextet with the hyperfine field of 3.6 T. In a trimer, each Fe^2?+? magnetic moment is supposed to be directed from Fe^2?+? to OH^???.     

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.     

Magnetism of (Fe0.93Ni0.07)2P studied using 57Fe Mössbauer spectroscopy

⁵⁷Fe Mössbauer spectroscopic measurements have been carried out on (Fe_0.93Ni_0.07)₂P in the temperature range 85–405 K. Obtained values of hyperfine field at the two metallic sites are slightly smaller than in Fe₂P. But the reduction is much less than as reported in Cr or Mn or Co substituted analogues of Fe₂P.     

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.     

Effect of pseudohalides in pentadentate-iron(III) complexes studied by DFT and Mössbauer spectroscopy

Mononuclear iron complexes in which the iron(III) ion is coordinated by a pentadentate Schiff base ligand L⁵ with two phenolate, two imino and one amino group can exhibit a spin crossover. In this contribution experimental results are presented for complexes with cyanate and thiocyanate as co-ligands. Furthermore, theoretical results of quantum chemical calculations of energies and entropies for the low-spin and high-spin state are shown and compared with Mössbauer results. We also demonstrate how the ligand field of the monodentate co-ligand influences the spin crossover energies and entropies in [Fe^IIIL⁵NCY] complexes.     

Practical aspects of Mössbauer spectroscopy instrumentation

The setting up and updating of a Mössbauer laboratory imply the acquisition and assembling of different units. Guidelines concerning either the construction or the acquisition of the various parts which compose a Mössbauer spectrometer are given in this paper.     

Mössbauer spectroscopy of 151 europium dicarboxylates

We have previously reported the stability of europium oxalate compared to ammonium europium bis-salen and europium benzoate. We now extend the dicoarboxylic acid chain of the oxalate by introducing additional-CH₂-groups in the dicarboxylate ligands by using malonate, succinate, glutarate and adipate. Additionally, we have examined the effect of alterations in the succinate dianion by introducing functional groups such as [C = C]in the case of the maleide and-OH group in the case of the malide. This study is an attempt to further characterize these compounds. Infrared spectra were used to characterize bridging and chelating dicarboxylates while Mössbauer spectroscopy measurements were used to gain better insight into the structure of heterocyclic “cages” containing two Eu^3?+? ions and two dianions.     

Observation of spin-lattice relaxations of dilute Fe3+ in MgO by Mössbauer spectroscopy

We present a method to describe the temperature dependence of emission Mössbauer spectra showing slow spin-lattice relaxations of Fe^3?+? in MgO single crystals, obtained after implantation of ⁵⁷Mn at ISOLDE/CERN. The analysis is based on the Blume-Tjon model for the line-shape of relaxing paramagnetic sextets with the spin relaxation rate, τ ^???1 as a parameter. The temperature dependent spin relaxation rate of Fe^3?+? in MgO is found to increase to ~10⁸ s^???1 at 647 K by assuming a relaxation rate of τ ^???1?< 10⁶ s^???1 at 77 K. The results are in accordance with those obtained by electron paramagnetic resonance spectroscopy demonstrating the possibility of retrieving spin-lattice relaxation rates of dilute Fe^3?+? from emission Mössbauer spectroscopy of Mn/Fe-implanted oxides.     

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 spectroscopy and magnetic studies of orientated textured Fe3O4 ferrofluid

Nano scale magnetite based ferrofluid is synthesized by chemical co pre cipitation technique and stabilized with oleic acid. Magnetization and viscosity measurements were used to optimize for texturing purpose. The freeze-textured ferrofluid in two configurations, namely, (1) field texture system (FTS) and (2) zero field texture system (ZTS) are investigated by magnetization measurements at 298 K and Mössbauer spectroscopy measurements at 77 and 298 K. These results are analysed on the basis of the contributions from collective superparamagnetic reversal and the strength of the inter particle interactions.     

67Zn Mössbauer spectroscopy

The 93.31-keV Mössbauer resonance in⁶⁷Zn is used to determine tiny changes of the transition energy. We first report on a gravitational redshift (GRS) experiment with⁶⁷GaZnO single crystal source and⁶⁷ZnO powder as absorber. The results on the GRS show that solid state effects which are difficult to control experimentally, in particular the extreme sensitivity of the electric field gradient tensor (efg) in⁶⁷ZnO to small external pressure, finally limit the accuracy in determining the GRS. The resonance has been further employed to investigate solid state properties of⁶⁷ZnO with high precision. At large pressures⁶⁷ZnO exhibits a phase transition from hep (wurtzite) to fcc (NaCl) structure. The changes of the efg and of the s-electron density θ(0) at the⁶⁷Zn nucleus with reduced unit cell volume show that covalency of the Zn-O bond plays and essential role. We have performed self-consistent Hartree-Pock cluster calculations to describe the experimental changes of θ(0) in detail.     

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 at ISOLDE

Applications of radioactive ion beams produced at the ISOLDE facility for Mössbauer studies of probe atoms in solids are presented. Examples are given for a site-selective incorporation on different substitutional sites in compound semiconductors by ion implantation and thermal annealing of the radiation damage resulting from the implantation. The interactions of the probe atoms with lattice defects created in the implantation process have been studied to elucidate likely causes for the site-selective implantation mechanism. The technique has enabled to determine the electronic densities at electrically active substitutional probe atoms, having shallow donor or acceptor states as well as states deeper in the band gap. The results are in good agreement with theoretical results from local density calculations. Methodological aspects of the Mössbauer emission techniques employed at ISOLDE are compared to alternative accelerator based techniques and the consequences of the application of different precursor isotopes to the ⁵⁷Fe Mössbauer isotope are treated in detail for ⁵⁷Fe in silicon. Finally, results obtained for the magnetic hyperfine interactions of 5 sp impurities associated with vacancies in ferromagnetic metals are discussed.     

Surface magnetism of β-FeO(OH) by Mössbauer spectroscopy

Fine particles of -FeO(OH) were prepared using the⁵⁶Fe isotope and the surfaces of the particles were coated with extremely thin⁵⁷Fe(III) layers. Mössbauer results show that the Fe(III) ions in the top surface layer are involved in the magnetic order and occupy two kinds of surface sites. Both of the two exchange field at surface sites, estimated from the temperature dependences of the hyperfine fields, are smaller than the bulk value. The decrease of exchange fields at the surface sites corresponds to the reduced number of neighboring magnetic ions at each site.     

Application of Mössbauer spectroscopy to the thermal decomposition of strontium and barium bis(CITRATO)Ferrates(III)

The thermal decomposition of M₃[Fe(cit)₂]₂ 4H₂O (M = Sr, Ba) has been studied isothermally and non-isothermally employing simultaneous (TG–DTG–DSC), XRD, IR, SEM and Mössbauer spectroscopic techniques. The anhydrous complexes decompose at 140–220°C to yield α-Fe₂O₃ and MC₅H₄O₅ (metal acetone-dicarboxylate) intermediates. The latter decomposes to respective carbonate at higher temperature. α-Fe₂O₃ and MCO₃ undergo a solid state reaction in the temperature range 400–430°C to yield Sr₂Fe₂O₅ and BaFe₂O₄ respectively. Finally above 600°C, a solid state reaction between these products and respective metal oxides leads to the formation of M₃Fe₂O_7???X showing simultaneous presence of Fe(III) and Fe(IV) species. These perovskite ferrites can exhibit electrical conductivity and dielectric properties. SEM analysis shows these ferrites to be nanosized with average particle diameter of 50–55 nm.