The Nonanuclear [Mo(IV){(CN)Fe(III)(3-ethoxy-saldptn)}8]Cl4 Complex Compound Exhibits Multiple Spin Transitions Observed by Mössbauer Spectroscopy

The hyperfine interactions at ¹⁸¹Ta ions on Fe³⁺ sites in α-Fe₂O₃ (hematite) were studied in the temperature range 11–1100 K by means of the perturbed angular correlation (PAC) technique. The ¹⁸¹Hf(β⁻)¹⁸¹Ta probe nuclei were introduced chemically into the sample during the preparation. The hyperfine interaction measurements allow to observe the magnetic phase transition and to characterize the supertransferred hyperfine magnetic field B_hf and the electric field gradient (EFG) at the impurity sites. The angles between B_hf and the principal axes of the EFG were determined. The Morin transition was also observed. The results are compared with those of similar experiments carried out using ¹¹¹Cd probe. ^aAlso at Comisión de Investigaciones Científicas de la Provincia de Buenos Aires, Argentina.     

Mössbauer study of the magnetic and electric hyperfine interaction of dilute57Fe impurities in rare earth metal hosts

The hyperfine interaction of dilute⁵⁷Fe in the rare earth (RE)metals Gd to Lu was investigated by Mössbauer measurements with⁵⁷Co doped RE sources. In all hosts well split, 2-lines spectra were observed at room temperature, with slight asymmetries of the line intensities in some cases. The quadrupole splitting eQV_zz/2 increases from 0.29 mm/sec for Gd to 0.50 mm/sec for Tb, and decreases by less than 10 % between Tb and Lu. Only about 10 % of the corresponding electric fieldgradient (EFG) can be accounted for by the ionic EFG on a substitutional RE site. The temperature dependence of the EFG was measured in the case of Tb. No variation within 3 percent was found between 300 K and 700 K. Measurements of the magnetic hyperfine interaction at low temperatures were carried out in Tb. The saturation field of⁵⁷Fe in this host is H_hf(FeTb;4.2 K)=25(2) KOe. The temperature dependence of the magnetic hyperfine field does not follow the host magnetization (T_c=220K) but vanishes at about 80 K. Similar anomalies of H_hf(T) have previously been observed for other transition element impurities in the RE ferromagnets.     

Effect of pressure on the valence state of Yb in YbPd2Si2

The intermediate valent behaviour of YbPd₂Si₂ has been studied under pressure in the temperature range from 1.2 K to 90 K by using the 84 keV Mössbauer transition in¹⁷⁰Yb. At 54 kbar and 4.2 K we obtain an increase of the electric field gradient (EFG) by a factor of 3. In addition, the EFG varies strongly with temperature, in contrast to the behaviour at ambient pressure. At 1.2 K a change of the hyperfine pattern is observed indicating a magnetic character of the Yb ion. These results provide evidence of a pressure induced change of the valence state close to 3+.Work supported by the Deutsche Forschungsgemeinschaft     

Hyperfine Interactions in CeT2Ge2 (T = Mn,Co) Heavy Fermions Compounds Measured by TDPAC

Time Differential Perturbed γ–γ Angular Correlation (TDPAC) technique was used to measure the magnetic hyperfine field at both Ge and Ce sites in CeMn₂Ge₂ and CeCo₂Ge₂ intermetallic compounds. The ¹¹¹In (¹¹¹Cd) probe nuclei was used to investigate the hyperfine interaction at Ge sites, while the ¹⁴⁰La (¹⁴⁰Ce) nuclei was used to measure the magnetic hyperfine field at Ce site. The present measurements cover the temperature ranges from 10–460 K for CeMn₂Ge₂ and 9–295 K for CeCo₂Ge₂, respectively. The result for ¹¹¹Cd probe showed two distinct electric quadrupole frequencies above magnetic transition temperatures, in both compounds and a combined interaction in the magnetic region. The temperature dependence of the magnetic hyperfine field at ¹¹¹Cd at Mn site for the CeMn₂Ge₂ compound showed a transition from ferromagnetic to antiferromagnetic phase around 320 K and from antiferromagnetic to paramagnetic phase at 420 K. While a small magnetic field was measured on ¹¹¹Cd at Co site, no magnetic field on ¹⁴⁰Ce site was observed in CeCo₂Ge₂. This revised version was published online in September 2006 with corrections to the Cover Date.     

Pac study of the hyperfine interactions in154Gd3+ in rare-earth-garnets

The attenuation of the anisotropy of the γ-γ angular correlation for a rare-earth ion in magnetic iron and non-magnetic aluminum rare-earth garnets is governed by the static hyperfine electric field gradient (EFG) produced by the surrounding ions and by the static and fluctuating hyperfine magnetic fields produced by the 4f electrons of the ion. The latter effect depends upon the correlation time (τ_c) of the 4f electrons which, in turn, is determined by the interaction of the ionic spin with lattice vibrations and other magnetic ions. In an attempt to determine the significance of spin-spin relaxation on τ_c, perturbed angular correlation (PAC) measurements were performed on the S-state ion¹⁵⁴Gd³⁺ because spin-lattice interactions were expected to be small. The time-integral attenuation coefficients of the 1274/123 keV γ-γ cascade in¹⁵⁴Gd were measured in the temperature region 4.2–650 K for¹⁵⁴Gd³⁺ incorporated in GdAlG, GdIG, YAlG, and YIG. Rotation measurements were also made on the same cascade in the iron garnets at room temperature with an applied magnetic field in the range 0–15 kg. Employing independent measurements and calculated estimates of the static hyperfine magnetic field and EFG, the observed data could be interpreted in terms of reasonable values of τ_c. The correlation times were found to range from about 0.13 ns in YIG to about 1.30 ns in YAlG with GdAlG having a value of approximately 0.71 ns. In the case of GdIG, a self-consistent analysis of the data required a value of the lattice EFG which was larger than that estimated from the nearest neighbor point-ion model. The correlation time in GdIG was then found to be the same as in YIG.     

Mössbauer studies of FexNbS2 (x = 0.25, 0.33 and 0.5)

Mössbauer studies of Fe_xNbS₂ (x = 0.25, 0.33 and 0.5) have been carried out for temperatures from 4.2K to about 715K. The iron exists in high spin divalent state for all the compositions. The temperature dependence of quadrupole splitting and center shift shows a reversible phase transition at about 600K and a possible disordering of Fe vacancies beyond this temperature for Fe_0.25NbS₂ and a reversible phase transition at 490K for Fe_0.5NbS₂. The hyperfine magnetic fields have been evaluated from the magnetically ordered spectra. The observed temperature dependent line intensities of the quadrupole doublet are attributable to the temperature dependence of the difference in the meansquare amplitude of vibrations parallel and perpendicular to the EFG axis.     

Study of combined magnetic and electric hyperfine interactions for cadmium in Dysprosium by time differential perturbed angular correlations

The combined magnetic and electric hyperfine interaction at the site of a¹¹¹Cd impurity in magnetically ordered Dysprosium has been investigated as a function of temperature by time differential perturbed angular correlation measurements. Three different phases have been found in metallic Dy with transition temperatures of 85 and 179 °K in agreement with the results of bulk material measurements. In the paramagnetic phase above 179 °K a pure electric quadrupole interaction has been observed. The various contributions to the electric fieldgradient are analyzed and it is shown, that the dominant contribution comes from the conduction electrons. In the ferromagnetic phase which extends from 0 to 85 °K the magnetic hyperfine field at the site of¹¹¹Cd has the same temperature dependence as the spontaneous magnetization. The value of the hyperfine field at 4.2 °K is ¦H _eff¦=(221 ± 4) kG. At 85 °K a transition to the antiferromagnetic phase of Dy occurs, which shows a hysteresis of the transition temperature. In the antiferromagnetic phase the temperature dependence of the hyperfine field deviates considerably from the magnetization curve. It is suggested that this deviation might be due to a temperature dependence of thes-f exchange interaction.     

Mixed hyperfine interactions and defect structure in magnesiowüstite Fe−Mg−O

An analysis of the 4.2 K spectra of Fe_xO (x∼0.91) and (Fe_0.4Mg_0.6)_xO is presented in which it is considered that because of the large electric field gradient at Fe²⁺ defect sites, the spectra cannot be described by Lorentzian sextets. It is assumed that the magnetic hyperfine field vector is oriented at random in the coordinate system defined by the EFG main axis, and that the EFG coordinate system is also distributed randomly. The simplifying assumption of the asymmetry parameter η=0 allows an analytical formula to be used to describe the complex spectra. Distributions of both magnetic hyperfine field and quadrupole interaction were progressively refined resulting in reasonable fits to the spectra with the main features being well reproduced. The magnetic hyperfine field distribution is rather broad with several features present while distinct values were obtained in the distribution of quadrupole interactions. These latter values are considered to correspond to the defect configurations around the Fe²⁺ sites. The distribution of hyperfine fields is considered to reflect the varying strengths of superexchange due to the high defect concentration as well as the effects of magnetic relaxation.     

Electronic and magnetic properties of the paramagnetic Twenty electron Fe(O) sandwich [C6(CH3)6]2 Fe from Mössbauer measurements and molecular orbital calculations

A Mössbauer study of the title paramagnetic Fe(O) complex was carried out from 4.2 K to 250 K. The electric field gradient (EFG) tensor was found to be temperature independent in accordance with the well isolated nature of state³A_2g. Measurements in an applied magnetic field of 6 T confirmed the paramagnetic nature (S=1) of the complex and showed the EFG tensor to be negative. From the thermal variation of the hyperfine field we determined the spin hamiltonian constant D=14 K and find the g-value to be close to the free electron value. Semi-empirical molecular orbital (MO) calculations were carried out with a modelized molecule of D_6h symmetry; results are in good agreement with the experimental values (for both the electronic and magnetic properties).     

Magnetism of Fe in SrFe2As2: Local investigation by time differential perturbed angular distribution (TDPAD) spectroscopy

Employing the γ-ray perturbed angular distribution technique, we have measured the magnetic hyperfine field of ⁵⁴Fe in tetragonal and orthorhombic structural phases of SrFe₂As₂. In the tetragonal phase, the magnetic response of ⁵⁴Fe shows Curie-Weiss type local susceptibility, indicating the presence of localized moment on Fe. The temperature dependence of the hyperfine field of ⁵⁴Fe reflects quasi-two dimensional first order magnetic transition at 200 K. Our data indicate that Fe moments in the magnetically ordered phase of SrFe₂As₂ may be canted out of the ab-plane.     

Hyperfine magnetic interactions of 57Fe nuclei in NaFeAs arsenide

The results of the Mössbauer effect studies of layered NaFeAs arsenide in a wide temperature range are presented. The measurements at T > T _N demonstrate that the main part (～90%) of iron atoms are in the low-spin state Fe²⁺. The other atoms can be attributed to the impurity NaFe₂As₂ phase or to the extended defects in NaFeAs. The structural phase transition (at T _S ≈ 55 K) does not produce any effect on hyperfine parameters (δ, Δ) of iron atoms. At T < T _N, the spectra exhibit the existence of a certain distribution of the hyperfine magnetic field (H _Fe) at ⁵⁷Fe nuclei, indicating the inhomogeneity of the magnetic environment around iron cations. The analysis of the temperature behavior of the distribution function p(H _Fe) allows us to determine the temperature of the magnetic phase transition (T _N = 46 ± 2 K). It has been found that the magnetic ordering in the iron sublattice has a two-dimensional type. The analysis of the H _Fe(T) dependence in the framework of the Bean-Rodbell model reveals a first-order magnetic phase transition accompanied by a drastic change in the electron contributions to the main component (V _ZZ ) and the asymmetry parameter (η) of the tensor describing the electric field gradient at ⁵⁷Fe nuclei.     

Low temperature 151Eu and 57Fe Mössbauer study of mechanically alloyed EuFeO3

Low temperature ⁵⁷Fe Mössbauer spectra of mechanically alloyed EuFeO₃ prepared by mechanical alloying depicts an interesting transformation in its hyperfine magnetic state, from a triple phase magnetic system at room temperature to a single phase ferromagnetic state at 20 K. The hyperfine magnetic field increased by 12% at 20 K from its room temperature. The isomer shift and quadrupole splitting values exhibit a peak around 200 K. Low temperature ¹⁵¹Eu Mössbauer measurements show that the line-width increased to its maximum value at 80 K which is 45% compared to its room temperature value not enough to suggest splitting.     

Production of spin polarized 12N through heavy ion reactions

The structural and magnetic properties of Ho substituted BiFeO₃ (BHFO) have been investigated using ⁵⁷Fe Mössbauer spectroscopy and X-Ray diffraction (XRD) as a function of temperature. The Mössbauer spectrum obtained at room temperature for the as-synthesized BHFO sample exhibits broadened features due to the hyperfine field distributions related to the local variation of the neighbourhood of Fe and the magnetic hyperfine splitting patterns are indicative of magnetic ordering, mostly probably screwed or slightly antiferromagnetic. The spectrum was fitted with two superimposed asymmetric sextets, with similar hyperfine magnetic fields of B_hf1 = 48.0(1) T and B_hf2 = 49.0(1) T, corresponding to rhombohedral BFO. The hyperfine fields of the magnetic components decreased systematically with increasing temperature to a ‘field distribution’ just below the Néel temperature, T_N ~ 600 K. At temperatures above 600 K, the spectral line associated with the Bi₂₅FeO₄₀ impurity phase dominates the spectra. This phase is confirmed by XRD measurements. From the temperature dependence of the site populations of the spectral components an average Debye temperature of θ _D = 240(80) K has been estimated.     

Hyperfine and magnetic properties of 19e− (electron reservoir) sandwiches of Fe(I), C5R5FeC6R6 (where R=H or CH3) and (C6(CH3)6)2Fe+: Mössbauer experiments and molecular orbital calculations

The four compounds C₅H₅FeC₆H₆, C₅H₅Fe(CH₃₎₆, C₅(CH₃₎₅FeC₆(CH₃₎₆ and (C₆(CH₃₎₆₎₂Fe⁺ were studied by Mössbauer spectroscopy on powders. On the basis of semi-empirical molecular orbital calculation (Iterative Extended Hückel with self-consistence of the charge) in which parameters derived from X-ray data are used, we have modelized the thermal behaviour of the electric field gradient (EFG) tensor from 4 K to 300 K. The reduction in magnitude of electronic observables (e.g. spin orbit coupling constant and EFG magnitude) gave evidence for a dynamic Jahn-Teller effect. Spectra in a high magnetic field (6 teslas) confirmed the paramagnetic behaviour of the compounds. The sign of the EFG tensor, the magnetic hyperfine field tensor and its orientation with respect to the EFG tensor were determined.     

The temperature dependence of the magnetic hyperfine field of tantalum in dysprosium

The temperature dependence of the magnetic and electric hyperfine interactions at the site of ¹⁸¹Ta impurities in polycrystalline Dy has been measured between 4.2 and 178 K using the time differential perturbed angular correlation technique. The value of the magnetic hyperfine field at 4.2 K is: |H_hf(TaDy)| = 212(9) kG The temperature dependence of the magnetic hyperfine field follows closely the prediction of the molecular field model.     

Effet Mössbauer sur les noyaux d'impuretes 119Sn4+ dans la matrice de VO2

The phase transition in VO₂ doped with 0.16 at.% Sn⁴⁺ was investigated by Mössbauer spectroscopy of ¹¹⁹Sn. Hyperfine magnetic fields were observed on ¹¹⁹Sn nuclei below the transition temperature. At 77 K the maximum hyperfine magnetic field was found to be H(0)_{77 K} = 120 ± 10 kOe The results obtained are discussed in terms of fine antiferromagnetic particles.     

Mössbauer effect study of Y(57FeMn)2

YMn₂ compound doped with⁵⁷Fe was investigated using⁵⁷Fe Mössbauer resonance in the temperature range 4.2–400 K. The magnetically split spectra were analyzed assuming two magnetically nonequivalent Fe sites with relative population dependent on iron concentration. In the transition temperature region a coexistence of the magnetic and nonmagnetic components was observed in the temperature span of about 50 K. A thermal hysteresis (of about 25 K) of the magnetic component confirms the first-order type magnetic transition. Temperature dependence of the hyperfine field of the magnetic component could be interpreted in terms of spin-fluctuation theory.     

Analysis of175Lu NMR data on dilute alloys of Lu in Tb and Dy

Results of Sano, Shimizu and Itoh on NMR frequencies of¹⁷⁵Lu in ferromagnetic Lu_0.02Tb_0.98 and Lu_0.02Dy_0.98 alloys are fitted by use of a model with five adjustable parameters. Two of these are related to the magnitude and asymmetry of the electric-field-gradient (EFG) tensor at a Lu nucleus, and three others specify the magnitude of the magnetic hyperfine field and its orientation with respect to the principal axes of the EFG tensor. For LuDy it is found that (i) the hyperfine field is tilted with respect to these axes, and (ii) the asymmetry of the EFG tensor differs in magnitude from published calculated values based on a point-change model. For LuTb at least one of these two statements is shown to be true. Tilting of the hyperfine field is consistent with inferences from neutron scattering data that the 4f moment is tipped away from the b axis in Tb metal.     

Magnetic Properties of Iron Clusters in Silver

Time differential perturbed γ-γ angular correlation technique was used to measure the magnetic hyperfine field (MHF) at Tb sites in the intermetallic compound Tb₃In₅ using the ¹⁴⁰La → ¹⁴⁰Ce nuclear probe. The measurements were carried out in the temperature range of 8 to 295 K. Two different temperature dependent magnetic frequencies were observed below 30 K, which were assigned as ¹⁴⁰Ce substituting the two inequivalent Tb sites in the orthorhombic structure of Tb₃In₅. The temperature dependence of MHF also shows a possible deviation from an expected Brillouin-like behavior for temperatures below 18 K. A Néel transition at 27 K was observed from magnetization measurements in the samples. The magnetization as a function of the applied magnetic field was measured at two temperatures, 5 and 40 K, and the results show antiferromagnetic and a typical paramagnetic behavior, respectively. In both cases it was not observed saturation under high magnetic field.