99Ru,61Ni,57Fe,and119Sn Mössbauer studies of Heusler alloys containing ruthenium

⁹⁹Ru,⁶¹Ni,⁵⁷Fe and¹¹⁹Sn Mössbauer spectroscopic studies were made on ternary intermetallic compounds containing ruthenium, Ru_xY_3?xZ (Y=Fe, Ni; Z=Si, Sn). In the system of Ru_xFe_3?xSi, two different hyperfine magnetic fields were observed at the⁹⁹Ru nuclei (H _hf[Ru]) in the range ofx≤1.0 and the magnitude of eachH _hf[Ru] was found to decrease with an increase in the ruthenium concentrationx. Both the⁹⁹Ru and¹¹⁹Sn Mössbauer spectra of Ru₂FeSn could be analyzed with two sets of magnetically split lines. The⁶¹Ni Mössbauer spectra of Ru₂NiSn were obtained at 5 and 77 K.     

Ratios of gI-factors and hyperfine structure anomalies of115Sn,117Sn and119Sn

The ratios of the g_I-factors of¹¹⁵Sn,¹¹⁷Sn and¹¹⁹Sn have been measured by the NMR method in different solutions which have large chemical shifts. No primary isotopic effect on the magnetic shielding was found within the error of 7·10^?7. Therefore the ratios have been used for the calculation of the hyperfine structure anomalies in the³P₁,³P₂ and¹D₂ atomic states of the given tin isotopes.     

119Sn and57Fe Mössbauer study of La2−x Sr x CuO4

Mössbauer absorption measurements were carried out for¹¹⁹Sn and⁵⁷Fe impurities in La₂CuO₄, La_1.85Sr_0.15CuO₄ and La_1.6Sr_0.4CuO₄. For all cases,⁵⁷Fe spectra at 4.2 K show magnetic hyperfine splittings. On the other hand, a magnetic hyperfine field at Sn nucleus is observed only in the case of La_1.85Sr_0.15CuO₄. The results indicate that the Cu magnetic spins are collectively fluctuating in the superconducting sample.     

Study of Au/SnO x –Al2O3 catalysts used in CO oxidation by in situ Mössbauer spectroscopy

The active catalytic components in tin oxide containing alumina-supported gold catalyst were examined by comparing and analysing the in situ Mössbauer spectra of the SnO _x –Al₂O₃ support and the 3 wt.% Au/SnO _x –Al₂O₃ catalyst (1.1 wt.% Sn, Au/Sn = 3:2 atomic ratio). Samples were prepared by using organometallic precursor of ¹¹⁹SnMe₄ (enriched). First tin was grafted to the alumina surface from the organometallic precursor compound. In the next step the grafted complexes were decomposed in flowing oxygen. Gold was deposited onto the SnO _x –Al₂O₃ support in the subsequent step. Analysis of in situ spectra shows that in Au/SnO _x –Al₂O₃ catalyst after activation in hydrogen at 620 K tin may occur in three different oxidation states [Sn (IV), Sn(II) and Sn(0)] simultaneously. The metallic tin is a component of the bimetallic AuSn alloy phase. Data presented provide the first evidence for the formation of alloy-type supported Sn–Au catalyst on alumina. Furthermore, from the spectra recorded at different temperatures, values of the Debye temperatures and recoilless fractions were also determined for the various species. The results show that in catalytic oxidation of carbon monoxide at room temperature the dominant part of Sn(II) and the AuSn alloy is oxidized.     

Magnetic interactions in119Sn substituted for Cu in antiferromagnetic and superconducting lamellar cuprates

Mössbauer Spectroscopy (MS) studies of¹¹⁹Sn were carried out in antiferromagnetic La₂(Cu_0.99Sn_0.01)O₄ (214) and in superconducting GdBa₂(Cu_0.99Sn_0.01)₃O₇(123). Non-magnetic Sn⁴⁺ substitutes for Cu if the right procedure for diffusing¹¹⁹SnO₂ in CuO is carried out. Studies performed in 214 show a large quadrupole splitting (QS) down to 120 K followed by an onset of a magnetic interaction reaching a saturation internal field ofH _eff=8.7(5) kOe atT=30K. From the combined magnetic-quadrupole interaction the angle θ formed byq _zz andH _eff, the η-parameter, and the sign ofQS were deduced and information on the local spin structure is derived. Studies conducted with the 123 material (T _c=90 K) reveal a broad unsplit line at temperatures down to 60 K followed by an abrupt onset of a magnetic interaction corresponding toH _eff (Sn)=8.3(1) kOe. The hyperfine fielddecreases with decreasing temperature reaching 6.0(1) kOe at 16 K. The onset of the magnetic interaction at the¹¹⁹Sn nucleus is explained as due to a local depletion of holes following the Sn⁴⁺ doping and a consequent quenching of the magnetic fluctuations in its vicinity.     

119Sn Mössbauer spectroscopy of U x Th1−x CoSn and UCoAl1−x Sn x

Magnetization and¹¹⁹Sn Mössbauer spectroscopy studies were performed on two pseudoternary systems, namely U _x Th_1?x CoSn and UCoAl_1?x Sn _x . Magnetic hyperfine fields on¹¹⁹Sn nuclei were found to be due to local surrounding of U atoms which carry magnetic moments. In pure UCoSn the valuesB _hf=8.66 T and μ_∪ satisfy the relationB _hf=6.75 μ_B found for a number of UTX compounds studied. Local surrounding effects are indicated by multicomponent spectra obtained for the two pseudoternary series.     

EPR study of Cu(II) dopant ions in single crystals of bis(l-asparaginato)Zn(II)

We report an electron paramagnetic resonance (EPR) study at 33.9 GHz and room temperature of oriented single crystal samples of bis(l-asparaginato)Zn(II) doped with Cu(II). The variation of the spectra with magnetic field orientation was measured in three crystal planes (a*b, bc and a*c, with a*=b×c). These spectra display two groups of four peaks arising from the hyperfine interaction with the I_Cu=3/2 nuclear spins of copper. They were assigned to Cu(II) ions in two lattice sites related by a 180° rotation around the b-crystal axis. The g and hyperfine coupling (A) tensors of the Cu(II) ions were evaluated from the single crystal data. Some indeterminacy in the assignment of the signals was avoided measuring the EPR spectrum of a powder sample. Their principal values are g₁=2.060(1), g₂=2.068(2), g₃=2.283(2), and A₁≈0.1×10⁻⁴, A₂=13×10⁻⁴ and A₃=165×10⁻⁴ cm⁻¹. The eigenvectors corresponding to g₃ and A₃ are coincident within the experimental error; the other eigenvectors are rotated 5.6° in the perpendicular plane. Considering the crystal structure of bis(l-asparaginato)Zn(II), our EPR results indicate that the Cu(II) impurities replace Zn(II) ions in the host crystal. We propose a molecular model based on the EPR data and the structural information, and analyse the results comparing the measured values with those obtained in similar systems.     

Local magnetic structure and anomalies of magnetic hyperfine interactions of57Fe and119Sn nuclei in lithium aluminium ferrites

The⁵⁷Fe and¹¹⁹Sn Mossbauer spectra of ordered ferrites Li_0.5Fe_2.5−xAl_xO₄∶Sn for 0.8<x<1.0 (the compensation point region) have been studied. The spin glass type magnetic structure with the spin canting angle depending on temperature and aluminium concentration is established. Anomalies in the temperature dependence of the hyperfine magnetic field at tin nuclei have been found near the compensation point of the ferrites     

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.     

Investigation of the effect of resonant environment (Mössbauer screen) on the observed half-life of the 119m1Sn isomer (E = 23.8 keV, T 1/2 ∼ 18 ns)

In order to analyze the effect of resonant environment on the γ decay of excited nuclei, the half-life of the ^119m1Sn isomer (E = 23.8 keV, T _1/2 ～ 18 ns), which appears from the decay of the ^119m2Sn state (E = 89 keV, T _1/2 ～ 293 d), has been measured by the e-γ coincidence method on samples consisting of the mixture of tin oxides containing the ¹¹⁹Sn stable nucleus and ^119m2Sn radioactive nuclei with various values of the ¹¹⁹SnO₂/^119m2SnO₂ ratio. For the samples, where this ratio is equal to 6.2 × 10⁴, 1.2 × 10⁶, 6.5 × 10⁶, and 1.7 × 10⁷, the half-life T _1/2is equal to 18.69(2), 18.71(2), 18.91(5), and 19.43(4) ns, respectively. For the reference sample (a metal with a ¹¹⁹Sn/^119m2Sn ratio of 1.5 × 10⁵), the value T _1/2 = 18.68(6) ns is obtained.     

Relative Lamb–Mössbauer factors of tin corrosion products

Variable temperature ¹¹⁹Sn Mössbauer spectroscopy was used to obtain relative Lamb–Mössbauer factors for three tin corrosion products: hydrated stannic oxide SnO₂·xH₂O, abhurite Sn₂₁O₆Cl₁₆(OH)₁₄, and tin hydroxysulfate Sn₃OSO₄(OH)₂. Their hyperfine parameters have also been investigated.     

Mössbauer characterization of tin dopant ions in the antiferromagnetic ilmenite MnTiO3

Mössbauer parameters of ¹¹⁹Sn diamagnetic dopant cations in an antiferromagnetic compound having the ilmenite structure are for the first time reported. The spectra reveal a well resolved hyperfine splitting pattern of combined magnetic and quadrupole interactions (at 5 K, δ=0.19 mm/s, H₁=52.5 kOe, eV_ZZQ_3/2=−0.80 mm/s, θ≈0°). This spectral component whose contribution (A₁=82%) represents more than four fifths of the total amount of the dopant (Sn/(Mn+Ti)=1/200) is assigned to Sn(IV) ions located in the bulk of MnTiO₃, on the Mn(II) site, and with a Mn(II) vacancy in their nearest surrounding. Two spectral components with minor contributions are also observed: one of them (H₂≈25 kOe, A₂=8%) can be assigned to Sn(IV) ions, in the MnTiO₃ lattice as well, on a site where they exhibit a weaker spin polarization (this site could be the Ti(IV) one) and the other (H₃=0 kOe, A₃=10%) to SnO₂ or/and Ti_1−xSn_xO₂ clusters. The Néel temperature of MnTiO₃ probed by the ¹¹⁹Sn dopant (T_N=69±2 K) agrees well with the values previously provided by ESR and antiferromagnetic resonance measurements. Variation of H₁ with temperature follows close the Brillouin function for S=5/2. No perturbation appears in the Mössbauer spectra around T=90 K where a broad peak, characteristic of 2D magnetic interactions, is observed on the static magnetic susceptibility curve.     

A 57Fe and 119Sn Mössbauer study of BaFe4Sn2O11

The Mössbauer spectrum of BaFe₄Sn₂O₁₁ has been recorded for both ⁵⁷Fe and ¹¹⁹Sn isotopes at a variety of temperatures. In the paramagnetic state the ⁵⁷Fe spectra are interpreted in terms of three iron environments. Magnetic ordering begins at 77 K and is virtually complete by 4.2 K to give an average magnetic hyperfine field of 504 kG. The ¹¹⁹Sn spectra also reflect the magnetic ordering and a magnetic hyperfine field of 45 kG is transferred to the tin nuclei.     

Hyperfine interactions and dynamics characteristics of 119Sn in xSnO2-(1-x)α-Fe2O3 nanoparticle system

The hyperfine interactions and dynamics aspects in nanoparticles system of the xSnO₂-(1-x)α-Fe₂O₃ (x = 0.0–1.0) have been investigated by ¹¹⁹Sn-Mössbauer and XRD techniques. The change revealed by the XRD (XRDSs) and Mössbauer spectra (MSs) vs. x was discussed in terms of the phase and lattice-dynamics changes. The evidences of the triple hyperfine magnetic fields’ distributions (MHFDs) and their dependencies x (<0.175) are discussed taking into account the super-transferred hyperfine interactions (STHI), the local disorder Sn^4?+?/Fe^3?+? around the tin isotope probe and the reduced dimension effect.     

Internal oxidation of sp-Impurities in silver studied by119Sn Mössbauer spectroscopy

The internal oxidation of the ion-implanted radioactive precursors¹¹⁹Cd and¹¹⁹Sb to the Mössbauer isotope¹¹⁹Sn in silver has been investigated. The oxidation is monitored by the intensity of a line in the Mössbauer spectra, which is characteristic of SnO₂ (δ=(0–0.23)mm/s relative to CaSnO₃, ΔEQ ≈ 0.5 mm/s, ? ≈ 220 K). This line is attributed to an internal oxidation of the implanted impurities by interstitially diffusing oxygen pairs. The formation and annealing kinetics of the impurity-oxygen complexes are interpreted in terms of the diffusion coefficients of oxygen and the sp-impurities in silver, respectively, and the reactivity between them. Comparison is made to Mössbauer experiments on SnAg alloys and to PAC measurements on¹¹¹cd in silver.     

Studies of EPR and ENDOR spectra of14N and15N label bis(2-hydroxyacetophenyl ketoxime)-63Cu(II) and-65Cu(II) complexes in disordered system

The EPR spectra of isotopic label bis(2-hydroxyacetophenyl ketoxime)-Cu(II) [N?Cu-HAP] complexes, such as¹⁴N?⁶³Cu-HAP,¹⁵N?⁶³Cu-HAP and¹⁴N?⁶⁵Cu-HAP in frozen THF solution below 77 K, and their ENDOR spectra in frozen DMSO/EtOH (5∶1) solution below 20 K were studied. The exact values of the components ofg-tensor, of hyperfine tensors of copper isotopes, and of superhyperfine interaction tensors of copper with nuclei of nitrogen isotopes and¹H nuclei, and of the¹⁴N nuclear quadrupolar moment coupling tensor were obtained. The bond parameters α, β, δ, γ and the corresponding energy levels of N?Cu-HAP complexes were calculated by using EPR and ENDOR data. It was shown that the unpaired, electron is delocalized not only to the nearest N atom but also to the H atom, of ligands, which is more far from the Cu ion.     

Co/Cu multilayers studied by using the119Sn probe

To observe spin polarization in nonmagnetic layers sandwiched by magnetic layers,¹¹⁹Sn Mössbauer spectra of [Co(20 Å)/Cu(20-x Å)/¹¹⁹Sn(1.5 Å)/Cu(x Å)] (x=0, 5 and 10) multilayers were measured. A magnetic fraction is observed in every spectrum, and the average hyperfine field ¯H _f at Sn nuclei in a Cu layer changes from 14 kOe (x=0) to 8 kOe (x=10). It was also observed that the polarization is greatly reduced by adding a Cr layer of only 2 Å to the Co/Cu interfaces. The spectrum of thex=10 film, measured under an external field of 30 kOe, cannot be interpreted without assuming magnetic fractions both in parallel and antiparallel to the external field, which indicates an oscillation of spin polarization in a Cu layer.     

57Fe and119Sn Mössbauer study of Ti-Containing highT c superconductors

⁵⁷Fe and¹¹⁹Sn Mössbauer spectroscopy as well as X-ray diffractometry were used to study Ti?Ca?Ba?Cu?O high T_c superconductors (T_c=106K) in the 4 to 300 K temperature range. X-ray diffractograms showed the dominant phase of these supercondutors to be 2-1-2-2 type. Three main iron sites were found and associalted with Fe in Cu sites in the real crystal. The dopublet with IS=0.25 mm/s and QS=0.7 mm/s at RT was attributed to the regular Cu site. No magnetic splitting was observed either in Sn or in Fe spectra taken even at 4 and 5K.     

Local31P and distant31P and195Pt ENDOR studies of powdered samples of Bis(O,O′-disubstituted-dithiophosphato)copper(II) complexes magnetically diluted in the corresponding Pd(II) and Pt(II) host lattices

ENDOR studies on bis(dithiophosphato)copper(II) complexes magnetically diluted in the corresponding Pd(II) and Pt(II) host lattices performed with the use of the method of “polycrystalline ENDOR crystallography” are reported. In these samples well resolved local³¹P (A_iso ca. 29 MHz and A_aniso ca. 0.9 MHz) as wel1 as distant³¹P (A _iso ca. 1.3 and 5.5 MHz and A_aniso ca. 0.2 and 0.4 MHz) and¹⁹⁵Pt (A_iso ca. 3.1 MHz and A_aniso ca. 0.2 MHz) ENDOR transitions are recorded. It is shown that the directions of the main values of A_aniso for all local³¹P and distant³¹P and¹⁹⁵Pt ENDOR transitions are parallel. Comparison of these results with those reported about the same complexes but diluted in other host lattices shows that there is no difference in the EPR and local³¹P ENDOR parameters thus suggesting that the structure of the paramagnetic complex remains unchanged. It is found that distant ENDOR transitions appear only in the case when the host lattice contains one molecule in the unit cell, i.e., when all molecules are parallel to each other. Using the obtained data from local and distant³¹P ENDOR transitions some structural features of Cu(dtp)₂ as well as Pd(dtp)₂ and Pt(dtp)₂ complexes are found for the first time.     

Simulation of the Electron Paramagnetic Resonance Spectrum of the Triplet Ground State Dimer Di-μ-(Pyridine N-Oxide)Bis[Bisnitrato(Pyridine N-Oxide)Copper(II)]

The EPR spectrum of the triplet ground state dimer di-μ-(pyridine N-oxide)bis[bisnitrato(pyridine N-oxide)copper(II)] has been reported recently¹. Of the very few triplet ground state copper(II) dimers with resolved metal hyperfine structure^2,3, the EPR spectrum of this complex is most complete. Previously, the analysis of the spectra of triplet ground state copper(II) complexes, in order to extract magnetic parameters, has been made using the equations reported by Wasserman et al.⁴ The best magnetic parameters should be obtained from a simulation of the experimental spectrum. We wish to report here the computer simulation of the EPR spectrum of a powdered sample of [Cu(II) (PYO)₂ (NO₃)₂]₂.