In-beam magnetization measurements of thin Fe foils and simultaneous observation of the transient magnetic field at Pd ions

The well established phenomenon of heavy ion beam induced attenuations of transient magnetic fields (TF) was studied by measuring the in-beam magnetization of bombarded Fe foils employing the magneto-optical Kerr-effect. Whereas the macroscopic magnetization did not show any deterioration, the simultaneously measured TF of recoiling¹⁰⁸Pd(2⁺) ions was found to be substantially attenuated.Dedicated to Prof. Dr. P. Kienle on the occasion of his 60th birthday     

New aspects of transient magnetic fields

Strong attenuations of transient magnetic fields are observed in Fe and Gd host for Coulomb excited^2HSi(2 ₁ ⁺ )- and²⁴Mg(2 ₁ ⁺ )-ions in their single-electron charge state as well as for multi-electron⁶²Ni(2 ₁ ⁺ ) ions. These effects are shown to be induced by the heavy ion beams used. The perturbations are found to be dynamic in nature and are attributed to a momentary loss of ferromagnetism of the host. This feature is also present in many earlier measurements using heavy ion beams but was not identified. The magnitude of the attenuations seems to be correlated with the energy loss of the beam ions in the ferromagnet.     

Isotropic paramagnetic hyperfine interaction: observed at matrix isolated57Fe ions in argon

A clean paramagnetic⁵⁷Fe Mössbauer spectrum due to an isotropic hyperfine interaction was observed at “almost free” Fe atoms in a frozen argon matrix. It was obtained by ion implantation λ⁵⁷Co in an argon matrix at 4.2 K and it is due to⁵⁹Fe⁺(3d⁷) ions in a magnetically isotropic Γ₆ or Γ₇ Kramers state. The hyperfine coupling constant of the free⁵⁷Fe⁺(3d⁷) ion in the nuclear groundstate is deduced to be A=5.0(3), 7.9(5) or 11.1(6) MHz, depending whether the Fe⁺(3d⁷) is in a J=9/2, 7/2 or 5/2 state respectively.     

Swift heavy ion irradiation-induced modifications in structural and electrical properties of Y3+-substituted yttrium iron garnet

The consequences of 50 MeV Li³⁺ ion irradiation (fluence: 5×10¹³ ions/cm²) on the structural and electrical properties of the Y_3+xFe_5?xO₁₂ (x=0.0, 0.2, 0.4 and 0.6) garnet system have been investigated over the temperature range of 300–673 K. It is found that the percentage formation of an additional yttrium orthoferrite phase observed along with the bcc garnet phase considerably reduces for x=0.4 and 0.6 compositions after swift heavy ion (SHI) irradiation. The nature of thermal variation of DC resistivity curves for x=0.0 and 0.2 compositions is different from that for x=0.4 and 0.6 compositions. The SHI irradiation influences the magnitude of DC resistivity and conduction mechanism for the single-phase compositions while for mixed-phase compositions they remain unaffected. The results have been explained in the light of replacement of magnetic (5μ_B), smaller (0.64 Å), Fe³⁺ ion by nonmagnetic (0μ_B), larger (0.89 Å), Y³⁺ ion, the presence of the yttrium orthoferrite phase and swift heavy ion irradiation-induced paramagnetic centers in the system.     

Investigation by EPR and ENDOR spectroscopy of the novel 4Fe ferredoxin fromPyrococcus furiosus

The hyperthermophilic archaeonPyrococcus furiosus contains a four-Fe ferredoxin (Pf- Fd) that differs from most other 4Fe-Fd’s in that its [Fe₄S₄] cluster is anchored to protein by only three cysteinyl residues.Pf- Fd also is of interest because in its reduced form, [Fe₄S₄]⁺, the cluster exhibits bothS = 1/2 andS = 3/2 spin states. Addition of excess cyanide ion converts the cluster exclusively to anS = 1/2 state (g₁ = 2.09, g₂ = 1.95, g₃ = 1.92), however dialysis restores the EPR signal of native reduced protein indicating that the cluster is not irreversibly altered by cyanide. Both the native protein and protein in the presence of excess cyanide ion (Pf- Fd 4Fe-CN) were investigated here using the techniques of electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy. In particular,Pf- Fd 4Fe-CN was investigated using¹³CN^? and C¹⁵N^? ligands.¹³C and¹⁵N ENDOR indicated that a single cyanide ion bound directly, with the cluster showing an unusually small contact interaction (a_iso(¹³C)～ ?3 MHz, a_iso(¹⁵N) ～ 0). This is in contrast to cyanide bound to monomeric low-spin Fe(III)-containing proteins such as transferrin and myoglobin, for which the¹³C hyperfine coupling has a large isotropic component (a_iso(¹³C) ≈ ?30 MHz). This small contact interaction is not due to low spin density of Fe, as⁵⁷Fe ENDOR of the singly and triply labeledPf- Fd 4FeCN isotopologs, [⁵⁷FeFe₃S₄]⁺ and [Fe⁵⁷Fe₃S₄]⁺, show hyperfine coupling characteristic for [Fe₄S₄]⁺ clusters, particularly for the Fe to which cyanide binds. Thus, the low spin density on¹³C is not due to low spin density on the Fe ion to which it binds. Further theoretical work is needed to explain the contrast between the strong electronic effect of cyanide ion binding with the low spin density on the ligand.     

57Fe conversion electron Mössbauer spectrometric study of boron and carbon ion implanted irons

Amorphous layers produced at the surface of iron by B⁺ and C⁺ implantation (50 kV, 1×10¹⁸ ions cm⁻²) were analyzed by CEMS. The CEM spectrum of B⁺ implanted layer was composed of broad doublet and sextet. Spread hyperfine field distribution, P(H), indicates the formation of extremely disordered FeB layer. Annealing at 400°C brought about precipitation of FeB, which was converted to Fe₂B by annealing at 500°C. The P(H) for C⁺ implanted iron was resolved to 3 subpeaks with H values of 11.0, 18.0 and 22.5 T. The amorphous FeC phase was strongly correlated to crystalline Fe₅C₂ and Fe₂C, which precipitated at 300°C and were transformed into Fe₃C at 500°C. The amorphous layer disappeared by annealing at 600°C.     

Hyperfine fields in the 5sp series studied by the low temperature nuclear orientation of83Rb,83Sr,85Sr and85Ym in iron

The hyperfine fields B_hf (RbFe), B_hf (SrFe) and B_hf (YFe) have been determined by the low temperature nuclear orientation of dilute samples of⁸³Rb,^83,85Sr and⁸⁵Y^m in an iron lattice to be B_hf (RbFe)=+54 (10) kG, B_hf (SrFe)=(?)100 (30) kG and B_hf (YFe)=?226 (10) kG. These results are compared with recent calculations for these fields (1), (2).     

Magnetic imaging at the atomic level

Magnetic contrast at the atomic level has been observed for the first time in scanning tunneling microscopy experiments on a magnetite (Fe₃O₄(001)) surface using in-situ prepared ferromagnetic Fe tips. A periodic corrugation with a 12 Å periodicity is clearly observed along the rows of FeB-sites which corresponds to the repeat period of Fe²⁺ and Fe³⁺ along these rows. This periodicity is not observed by using non-magneticW tips although the rows of FeB-sites can be resolved as well. The magnetic contrast observed with Fe tips is attributed to the different spin configurations of the magnetic ions Fe²⁺ and Fe³⁺ in Fe₃O₄.     

Local structure of Fe70Cr15B15 X-ray amorphous alloy

The local atomic and magnetic structure of Fe₇₀Cr₁₅B₁₅ X-ray amorphous alloy is studied by means of ¹¹B nuclear magnetic resonance (NMR) and ⁵⁷Fe Mössbauer spectroscopy. It is determined that Fe₈₅B₁₅ and Fe₇₀Cr₁₅B₁₅ X-ray amorphous alloys consist of microregions (nanocrystals) with short-range orders of t-Fe₃B and α-Fe phases. It was found out that chromium atoms in the Fe₇₀Cr₁₅B₁₅ X-ray amorphous alloy are evenly distributed in these two nanocrystals, forming t-(Fe,Cr)₃B and α-Fe(Cr) phases.     

Atomic and magnetic structures of Fe<Subscript>70</Subscript>Al<Subscript>5</Subscript>B<Subscript>25</Subscript> amorphous alloys

The short-range order around boron, aluminum, and iron atoms in Fe₇₅B₂₅ and Fe₇₀Al₅B₂₅ amorphous alloys has been studied by ¹¹B and ²⁷Al nuclear magnetic resonance at 4.2 K and ⁵⁷Fe Mössbauer spectroscopy at 87 and 295 K. The average magnetic moment of iron atoms μ(Fe) in these alloys has been measured by a vibrating sample magnetometer. It has been revealed that the substitution of aluminum atoms for iron atoms does not disturb μ(Fe) in the Fe₇₀Al₅B₂₅ alloy, gives rise to an additional contribution to the ¹¹B NMR spectrum in the low-frequency range, and shifts maxima of the distribution of hyperfine fields at the ⁵⁷Fe nuclei. In the Fe₇₀Al₅B₂₅ amorphous alloy, the aluminum atoms substitute for iron atoms in the nearest coordination shells of boron and iron atoms. This alloy consists of nanoclusters in which boron and iron atoms have a short-range order of the tetragonal Fe₃B phase type.     

Ab-initio calculation of electronic structure of partially inverted manganese ferrite

Electronic structure of manganese ferrite is calculated using the density functional theory. Partially inverted structure with the inversion parameter y=0.0625 is considered, using four different supercells (Mn₁₅Fe)_A[Fe₃₁Mn]_BO₆₄ that differ in relative position of Fe_A and Mn_B. The crystal structure was optimized by minimizing the forces acting on the atoms. The spin magnetic moments m of Mn and Fe ions depend to some extent on their position in the supercell, but we found that in all cases m(Mn_B) is considerably smaller (by approx. one Bohr magneton) than m(Mn_A). This indicates strongly that the formal valence of Mn_B is 3+. Trivalent manganese in an octahedral position is expected to exhibit a Jahn–Teller effect and corresponding analysis was performed. No pronounced localization of the extra electron in the octahedral sublattice that would represent the Fe²⁺ ion was found.     

Perturbed αγ-angular correlations in the decay of228Th

At external magnetic fields between 1.3 and 22.5 kG the integral αγ-angular correlations of theO ⁺(α)2⁺(γ)O ⁺ cascades from the ground states of²²⁸Th and²²⁴Ra respectively implanted into iron and aluminum lattices have been studied. The data were analyzed assuming different additional time dependent and static perturbations. The rotation of the angular correlation for Ra in Al proved independent of these assumptions. Therefore ag-factor of the 84.4 keV 2⁺ state in²²⁴Rag=0.46 (11) could be derived. Although static electric interactions seem the most probable cause for the attenuations observed for Ra and Rn implanted into Fe it was found that the two parameter Abragam and Pound theory better reproduces the data than the one parameter static perturbations. Therefore the hyperfine fields experienced by Ra and Rn in Fe were derived using Abragam and Pound theory to beH _HF(RaFe)=?127(31) kG andH _HF(RnFe)=1095 kG.     

Optical characterization of the phosphate glasses containing pair transition ions

The paper deals with optical and electronic properties of the aluminophosphate glasses containing Fe–Mn and Fe–Cr ion pairs in different concentration. The influence of the mixed alkali ions over the electronic properties has been investigated. The optical behavior (optical transmission) of the glass samples has been studied by UV-VIS spectroscopy and the refractive index dependency on wavelength has been discussed. The transmission spectra show features specific for the doping transition ions (TM), revealing different oxidation states of iron (Fe²⁺/Fe³⁺), manganese (Mn²⁺/Mn³⁺) and chromium (Cr³⁺/Cr⁶⁺) in the vitreous network. Mössbauer spectroscopy offers information regarding the TM oxidation states, redox processes and the iron coordination symmetry in the vitreous network. In the case of Fe–Mn doped glasses, the percentage of Fe²⁺ is about 40% and a doubled iron content leads to an increasing of Fe²⁺ percentage up to 53%. The replacing of lithium ions by natrium ions (mixed alkali effect) provides an increasing of the Fe²⁺ percentage up to 56%. The occurrence of the tetrahedral or octahedral symmetry of Fe²⁺ ions bonded by O^2? ions depends on the transition ion nature and Li⁺/Na⁺ ratio. Infrared absorption spectra of the pair transition ions-doped aluminophosphate glasses reveal optical phonons specific for the phosphate glass matrix.     

Measurements of the hyperfine magnetic fields at Ta and Fe in the Laves compounds (Zrx Hf1−x)Fe2 for 0≤x≤1

The hyperfine magnetic fields at¹⁸¹Ta and⁵⁷Fe in the ferromagnetic Laves intermetallic compounds (Zr_xHf_1?x)Fe₂ (0≤x≤1) have been measured by the methods of TDPAC and Mössbauer effect, respectively, and shown to be practically independent of x at x≥0.4. An average value B_hf (Ta)=?6.52 T at 300 K was obtained for samples with x≥0.4, and ?14.2 T for pure HfFe₂ in the hexagonal C14 modification. For 0hf(Ta) in (Zr_0.9 Hf_0.1)Fe₂ from that for B_hf (Fe) and the bulk magnetization was confirmed, studied in detail, and shown to exist for all x≥0.4. The temperature dependence of B_hf(Ta) in HfFe₂ was close to that of B_hf (Fe).     

Short range order of the amorphous Fe−B powders prepared by borohydride reduction

Ultrafine Fe?B amorphous alloy powders were prepared by reducing Fe²⁺ ions using KBH₄ and NaBH₄ in aqueous solution. Adjusting technological factors, the amorphous powders around the composition of Fe₆₅B₃₅ can be easily obtained, but in the vicinity of eutectic point (Fe₈₀B₂₀) a certain amount of α-Fe often appears in the samples. From the Mössbauer spectrum, the crystallization products of the Fe₆₃B₃₇ amorphous powder are α-Fe and Fe₂B phases. The measurement of¹¹B spin echo nuclear magnetic resonance (NMR) at 8K showed that Fe₂B-like and Fe₃B-like short range orders (SRO) exist in the amorphous powder of Fe₇₆B₂₄.     

Mössbauer study of ultrafine amorphous Fe−B alloys

The chemical composition of ultrafine amorphous Fe−B powders prepared by a chemical reduction depends on the mixed molar ratio of KBH₄ to Fe ions. We propose the following reaction processes for the formation of ultrafine Fe−B powders: (1) 4Fe²⁺+2BH₄₋+6OH⁻→2Fe₂B+6H₂O+H₂ and (2) 4Fe²⁺+2BH₄₋+7OH⁻→2Fe₃B+Fe+BO₂+5H₂O+5/2H₂.     

Vibrations and chemical states of iron ions in soda‐lime glasses determined by element‐specific X‐ray analyses

We systematically study medium‐range structures including more than three neighboring atoms around iron ions (Fe²⁺ and Fe³⁺) in soda‐lime glass samples with low iron oxide concentrations (M_Fe2O3) and a wide number ratio of Fe²⁺ to all iron ions (Fe²⁺/Σ_nFe). The precise medium‐range structures around iron ions in glass have not yet been revealed because of a lack of the appropriate measurement methods. To avoid this problem, we used element‐specific nuclear resonant inelastic scattering (NRIS) with synchrotron X‐rays to observe the vibrations of iron ions (⁵⁷Fe). The vibrations are related to medium‐range structures with more than three neighboring atoms and to the potential asymmetry and the coordination environment, around iron ions. The NRIS method has high sensitivity and can measure over a wide concentration range. Linear combination fitting of the X‐ray absorption fine structure spectra, which measures only the first neighbors but is a faster than using the NRIS method, was also used additionally. A systematically produced set of glasses with 0.015–5 wt% M_Fe2O3 and 0–0.85 Fe²⁺/Σ_nFe was measured with these methods. It was found that the soda‐lime glass possessed two different medium‐range structures with different iron ion valences (~2+ or ~3+), which were determined by the Fe²⁺/Σ_nFe, and that these structures were generated during production of the glass. Moreover, these medium‐range structures were the same from 0.015 to 5 wt% M_Fe2O3.     

Microstructures and multiferroic properties of textured Bi0.8La0.2FeO3 thin films

La-substituted BiFeO₃, Bi_0.8La_0.2FeO₃, thin films were fabricated on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition. X-ray diffraction and high-resolution transmission electron microscope were used to analyze the structures of the films. The results show the films fabricated under optimized growth condition are (0 1 2) textured. X-ray photoemission spectroscopy results indicate that the oxidation state of Fe ion is Fe³⁺ in the films without detectable Fe²⁺. The films show low leakage current and excellent dielectric characters. Multiferroic properties with a remnant ferroelectric polarization of 5.2 μC/cm² and a remanent magnetization of 0.02 μ_B/Fe were established. These results have some implications for further research.     

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^???.     

A polyhedron model for the spinel systems LI x Fe1−x CR2O4

Mössbauer spectra of the system Li⁺ _xFe²⁺ _1?2xFe³⁺ _x[Cr₂]O₄ measured at 150 K consist of one Fe(III) absorption and several Fe(II) doublets. An explanation was able by use of a statistical model of the Fe(II) environments.