Magnetism of ErAgSn studied by 119Sn Mössbauer spectroscopy

Antiferromagnetic ErAgSn compound was investigated in detail by ¹¹⁹Sn Mössbauer spectroscopy in a temperature range between 2.2 and 300 K. The ¹¹⁹Sn spectra recorded below 4.2 K can be well fitted with a single main magnetic component in agreement with recent neutron diffraction studies [1]. A broad distribution of magnetic hyperfine fields observed above 4.2 K and enhanced spin correlations among Er³⁺ ions at T > T _N = 5.6 K are the remarkable features of the investigated system.     

Local order of icosahedral quasicrystals studied by Mössbauer spectroscopy

Thermodynamically stable Al-Cu-Fe and Fe-doped ferromagnetic Al-Cu-Ge-Mn icosahedral quasicrystals are studied by⁵⁷Fe transmission Mössbauer spectroscopy and X-ray diffraction experiments. Al₆₅Cu₂₀Fe₁₅ quasicrystalline alloy was subjected to a mechanical grinding (MG) for up to 800 hours in a ball mill. Presence of the amorphous phase which co-exists with the quasicrystalline one is revealed in the early stage of MG. Mössbauer measurements were performed on icosahedral Al₄₀Cu_10–x Ge₂₅Mn₂₅Fe _x quasicrystal (x0.1; 3) in a temperature range from 10 K to 548 K. It was found that a magnetic transition occurs at about 30 K which is far belowT _c reported in the literature. It is concluded that AlGeMn ferromagnet which is present in the samples does not affect the magnetic transition observed and the transition is an intrinsic property of the Al-Cu-Ge-Mn host alloy.Samples of icosahedral quasicrystals were kindly provided by Profs. A. Inoue, T. Masumoto and P. H. Shingu. Ball milling was performed in Kyoto University by a courtesy of Prof. P. H. Shingu. This work was supported by the project for priority areas on properties of quasicrystals (No. 01630003) from the Japanese Ministry of Education, Science and Culture.     

Dynamics of iron in Fe-porphyrin aggregates studied by X-ray absorption and Mössbauer spectroscopy

The iron-porphyrin aggregates were studied by optical absorption and fluorescence method, infrared spectroscopy, X-ray absorption and Mössbauer spectroscopy. The aggregation of porphyrin molecules strengthens the Fe-ligands bonds and accelerates the spin-spin relaxations. A significant speeding-up of relaxation was observed with lowering the temperature down to 25 K. The comparison of the EXAFS (Extended X-ray Absorption Fine Structure) and Mössbauer spectroscopy results enabled some separation of the individual Fe vibration from its collective movement with ligands.     

Iron-metal multilayers studied by Mössbauer spectroscopy,RBS and X-ray diffraction

Fe/M (M = Ag, Zn and Sn) multilayers prepared by a vacuum evaporation method are studied by Mössbauer spectroscopy (MS), Rutherford backscattering spectroscopy (RBS) and X-ray diffraction (XRD). For the case of an M = Ag multilayer, MS reveals that Fe in the multilayer remains as an-phase down to the layer thickness of 10 nm. This result is in agreement with the RBS result that Fe and Ag form a completely discrete layer structure without any mutual mixing. For the case of M = Zn and Sn, RBS reveals that a considerable mixing has taken place between Fe and Sn during the specimen preparation. MS on Fe/Sn specimens with different layer thickness shows that an alloy phase of about 5 nm thickness is formed at the interface. Structural as well as magnetic properties of the alloy phase are discussed based on MS at different temperatures and on reported results of the intermetallic compound FeSn.     

Hydrogenation of FeCoZr–Al2O3 nanocomposites studied by Mössbauer spectroscopy and magnetometry

Hydrogenation effects on crystalline and magnetic structure of nanocomposites (FeCoZr) _x (Al₂O₃)_100???x , 38?≤?x?≤?63 at.% are studied by ⁵⁷Fe Mössbauer spectroscopy and magnetometry. Variations of local structure, blocking temperature and mean FeCoZr nanoparticles’ volume are discussed with respect to (i) composition and (ii) two competing processes—H₂ incorporation and annealing—occurred during treatment in H₂ plasma.     

Gold-surface binding of molecular switches studied by M?ssbauer spectroscopy

The nonanuclear coordination compound [Mo^IV{(CN)Fe^III(3-methyl-saldptn)}₈]Cl₄ exhibits multiple spin transitions (3-methyl-saldptn = N,N′-bis(3′′-methyl-2′′-hydroxy-benzyliden)-1,7-diamino-4-azaheptane). This spin crossover cluster is bound via a self-assembled monolayer onto a two dimensional array gold surface. M?ssbauer spectroscopy indicates that the thermally and optically induced spin crossover of the compound is maintained. Thereby, the foundation for its potential practical application (e.g. in the field of information storage) was laid.     

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.     

Structural evolution of glutathionate-protected gold clusters studied by means of 197 Au Mössbauer spectroscopy

¹⁹⁷Au Mössbauer spectra of a series of glutathionate-protected gold clusters, Au _n (SG) _m , with n = 10 ? ~55, were re-analyzed to understand the structure evolution behavior. The numbers of gold atoms coordinated by different numbers (0, 1, and 2) of the GS ligands were successfully determined by assuming individual isomer shifts and quadrupole splittings for the three sites in Au₂₅(SG)₁₈ (Tsukuda et al., Chem Lett 40:1292, 2011). The analysis revealed the drastic structural evolution of Au _n (SG) _m in the range of n = 10 ? ~55. In Au₁₀(SG)₁₀, all the gold atoms are bonded to GS ligands, indicating –Au–S(G)– cyclic structures. A catenane structure was proposed for Au₁₀(SG)₁₀. At n = 25, a single Au atom without the GS ligation appeared, consistent with the formation of an icosahedral Au₁₃ core protected by six staples, –S(G)–[Au–S(G)–]₂. At n = 39, it is considered that Au₃₉(SG)₂₄ has a similar structure to that of Au₃₈(SC₂H₄Ph)₂₄ with face-fused bi-icosahedral Au₂₃ core.     

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.     

Carrier mobility of iron oxide nanoparticles supported on ferroelectrics studied by Mössbauer spectroscopy

⁵⁷Fe Mössbauer spectroscopy was performed on two types of Fe oxide nanoparticles supported on a typical ferroelectric, BaTiO3. It was found that the valence state of FeO nanoparticles changed to a mixed 2+/3+ state at high temperature where BaTiO₃ shows paraelectric behaviour. We attribute this phenomenon to the fluctuation of electric dipoles which realizes carrier injection into the Fe oxides. This is the first report which discusses a dynamical valence state of transition metal oxides supported on ferroelectrics.     

Mössbauer spectroscopy of lanthanum and holmium ferrites

PrRh₂Si₂ is highly anisotropic Ising-type antiferromagnetic system. The ordering temperature (T _N~ 68 K) of PrRh₂Si₂ is exceptionally high on the de-Gennes scale in the family of RRh₂Si₂ (R = rare earths). The reason for this anomalous behaviour is not clear. It is believed that the presence of uniaxial anisotropy assists in enhancing the T _N. The Mössbauer study was performed on a 10% Fe-doped PrRh₂Si₂ sample to understand the magnetic coupling between different sites of PrRh₂Si₂. The Mössbauer spectra together with the magnetic susceptibility data suggest that the magnetic coupling in PrRh₂Si₂ is provided mainly by the RKKY interaction between Pr-moments.     

Characterisation of synthetic trioctahedral micas by Mössbauer spectroscopy

Trioctahedral potassium micas |K}[M₃]〈T₄〉O₁₀(OH)₂ have been synthesized by hydrothermal techniques with various cationic substitutions in the octahedral and the tetrahedral sheet. Taking annite |K}[Fe ₃ ²⁺ ]〈AlSi₃〉O₁₀(OH)₂ as the reference mineral, [Fe²] was replaced by [Mg²] and [Ni²], 〈Al³⁺〉 by 〈Fe³⁺〉 and finally [Fe²⁺] + 〈Si⁴⁺〉 by [Al³⁺] + 〈Al³⁺〉. Mössbauer spectra were evaluated in terms of quadrupole splitting distributions (QSDs) using three generalized sites for 〈Fe³⁺〉, [Fe³⁺] and [Fe²]. Annites, nominally free of 〈Fe³⁺〉, show a lower limit of [Fe³⁺]/Fe _tot of 0.10, which stabilizes the structure. The ferrous iron, [Fe²], QSD consists of two main components. In some of the solid solution series, there is strong experimental evidence for a third ferrous component, particularly at higher [Al³⁺] contents. This third component is centered at low quadrupole splittings and may be assigned to a defect [Fe²] site, forming 1:2 structures with two neighbouring trivalent octahedral cations. For charge compensation one OH^? is replaced by O^2? for each [M³⁺] cation. The ferrous QSDs vary systematically with chemical composition. Compared to those of annite, the QSD parameters (mean quadrupole splitting 〈QS〉 and quadrupole splitting with maximum probability, QS _peak ) are shifted towards higher values with increasing [Mg²] and [Ni²] contents, and decrease slightly with increasing content of trivalent cations. These trends can be interpreted in terms of changes in the local environment around the Fe probe nucleus, i.e., in terms of decreasing or increasing distortions from the ideal octahedral configurations.     

Fe/Dy artificial multilayered films studied by57Fe Mössbauer spectroscopy

Magnetic properties of multilayered Fe/Dy films with artificial superstructures have been investigated by⁵⁷Fe Mössbauer spectroscopy. Doublet peaks are observed at room temperature when the Fe layer is thinner than 20Å. Mössbauer spectra for thicker Fe layers correspond to α-Fe spectra. In certain samples, i.e. [Fe(44Å)/Dy(6Å)], a gradual spin reorientation takes place, which is evidenced from the change of relative intensities of Δm=0 lines with decreasing temperature.     

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.     

Effect of pressure on Néel temperature and hyperfine interactions in EuTe studied by Mössbauer spectroscopy

The pressure dependence of the Néel temperature T_N, the isomer shift S and the magnetic hyperfine field B_hf were measured in EuTe up to 60 kbar by means of the 22 keV Mössbauer resonance of ¹⁵¹Eu. A smooth increase of T_N was found, which yields λ_m = − dlnT_N/dlnV = 0.6(3). The variation of T_N and B_hf with pressure are discussed in terms of the exchange parameter J₂.     

Crystal-chemistry aspects and electric-field-gradient (EFG) dispersion in Ca-gallogermanate-type structures studied by Mössbauer spectroscopy

The crystal field disorder in some trigonal germanates of the type X_3-yLn_yFe_2+yGe_4-yO₁₄ (X = Ba, Sr; Ln = La, Nd; y = 0, 1) is studied by ⁵⁷Fe M?ssbauer effect. The dispersion of the electric field gradient (EFG) at the octahedral sites of these compounds is investigated. A correlation of the experimental and calculated EFG data with some crystal-chemistry aspects is presented. Received 3 February 1999     

Crystal field effects in Tm2M17 compounds studied by 169Tm Mössbauer spectroscopy

¹⁶⁹Tm Mössbauer spectra of the compounds Tm₂Fe₁₇ and Tm₂Co₁₇ were measured at various temperatures between 4.2 and 300 K. The spectra were analysed in terms of crystal fields and exchange fields and the presence of two crystallographically nonequivalent Tm sites in these compounds. The crystal field parameters derived from this analysis were used to derive approximate values of the anisotropy constants of these materials.