Mössbauer study of very dilute Pd(Fe) alloys at very low temperatures

The magnetic behaviour of very dilute (7 ppm and 0.6 ppm) Pd(Fe) alloys has been studied by Mössbauer spectroscopy in external fields up to 6 T in the temperature range between 0.018 and 300 K. No magnetic ordering was observed even at the lowest temperature. Above 0.067 K the magnetization exhibits free-spin behaviour. The saturation moment was found to be independent of temperature. Magnetic hyperfine patterns observed below 0.067 K were interpreted in terms of paramagnetic hyperfine interactions in the regime of slow electronic relaxation.     

Neutron powder diffraction investigation on the crystal and magnetic structure of (Ho(0.50+x)Ca(0.50-x))(Mn(1-x)Cr(x))O3

The crystal and magnetic structure of (Ho(0.50+x)Ca(0.50-x))(Mn(1-x)Cr(x))O(3) (x = 0.00, 0.01, 0.02, 0.03) has been investigated between 5 and 300 K by means of neutron powder diffraction followed by Rietveld refinement and dc magnetic measurements. During cooling an orthorhombic to monoclinic phase transition occurs on account of the charge and orbital ordering taking place in the Mn sub-lattice; at low temperature phase separation takes place and the main monoclinic phase coexists with a secondary orthorhombic phase, whose amount slightly increases with the increase of Cr content. Cr(3+) is not involved in orbital ordering or superexchange interactions. The charge and magnetic ordering are decoupled: the Mn moments order according to a CE-type structure in all samples.     

Large orbital moments and internal magnetic fields in lithium nitridoferrate(I)

The iron nitridometalates Li2[(Li(1-x)Fe(I)(x))N] display ferromagnetic ordering and spin freezing. Large magnetic moments up to 5.0mu(B)/Fe are found in the magnetization. In M?ssbauer effect studies huge hyperfine magnetic fields up to 696 kOe are observed at specific Fe sites. These extraordinary fields and moments originate in an unusual ligand field splitting for those Fe species leading [within local spin density approximation (LSDA)] to a localized orbitally degenerate doublet. Including spin-orbit interaction and strong intra-atomic electron correlation (LDA+SO+U) gives rise to a large orbital momentum.     

M?ssbauer study of the '11' iron-based superconductors parent compound Fe(1+x)Te

(57)Fe M?ssbauer spectroscopy was applied to investigate the superconductor parent compound Fe(1+x)Te for x?=?0.06, 0.10, 0.14, 0.18 within the temperature range 4.2-300?K. A spin density wave (SDW) within the iron atoms occupying regular tetrahedral sites was observed, with the square root of the mean square amplitude at 4.2?K varying between 9.7 and 15.7?T with increasing x. Three additional magnetic spectral components appeared due to the interstitial iron distributed over available sites between the Fe-Te layers. The excess iron showed hyperfine fields at approximately 16, 21 and 49?T for three respective components at 4.2?K. The component with a large field of 49?T indicated the presence of isolated iron atoms with large localized magnetic moments in interstitial positions. Magnetic ordering of the interstitial iron disappeared in accordance with the fallout of the SDW with increasing temperature.     

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).     

Doping dependent evolution of magnetism and superconductivity in Eu(1-x)K(x)Fe2As2 (x = 0-1) and temperature dependence of the lower critical field H(c1)

We have synthesized polycrystalline samples of Eu(1-x)K(x)Fe2As2 (x = 0-1) and carried out systematic characterization using x-ray diffraction, ac and dc magnetic susceptibility, and electrical resistivity measurements. A clear signature of the coexistence of a superconducting transition (T(c) = 5.5 K) with spin density wave (SDW) ordering is observed in our underdoped sample with x = 0.15. The SDW transition disappears completely for the x = 0.3 sample and superconductivity arises below 20 K. The superconducting transition temperature Tc increases with increase in the K content and a maximum Tc = 33 K is reached for x = 0.5, beyond which it decreases again. The doping dependent Tx phase diagram is extracted from the magnetic and electrical transport data. It is found that magnetic ordering of Eu moments coexists with the superconductivity up to x = 0.6. The isothermal magnetization data taken at 2 K for the doped samples suggest the 2+ valence state of the Eu ions. We also present the temperature dependence of the lower critical field H(c1) of the superconducting polycrystalline samples. The values of H(c1)(0) obtained for x = 0.3, 0.5, and 0.7 after taking the demagnetization factor into account are 202, 330, and 212 Oe, respectively. The London penetration depth λ(T) calculated from the lower critical field does not show exponential dependence at low temperature, as would be expected for a fully gapped clean s-wave superconductor. In contrast, it shows a T2 power law feature up to T = 0.3Tc, as observed in Ba(1-x)K(x)Fe2As2 and BaFe(2-x)Co(x)As2.     

Mössbauer investigation of hexagonal tungsten bronze type FeIII fluorides: (H2O)0.33 FeF3 and anhydrous FeF3

The new HTB (Hexagonal Tungsten Bronze) phases of FeF₃ and (H₂O)_0.33 FeF₃ have been characterized by ⁵⁷Fe Mössbauer spectroscopy; they have saturation hyperfine fields of (577 ±3) and (560±3) kOe and magnetic ordering temperatures (97±2) and (128.7 ± 0.5) K, respectively. The magnetic ordering temperature and the electric hyperfine interactions on iron are sensitive to the presence of zeolitic water in the system. Hydrolysed samples have also been investigated.     

Phase transitions and crystal-field and exchange interactions in TbFe3(BO3)4 as seen via optical spectroscopy

High-resolution polarized broadband (1800-23?000?cm(-1)) optical absorption spectra of Tb(3+) in TbFe(3)(BO(3))(4) single crystals are studied between room temperature and 4.2?K. The spectral signatures of the structural (R32-P3(1)21, T(S )?=?192?K) and magnetic (T(N )?=?41?K) phase transitions are found and analyzed. Energies and symmetries of the Tb(3+) crystal-field (CF) levels were determined for both the high-temperature R32 and the low-temperature P3(1)21 structures of TbFe(3)(BO(3))(4) and compared with the calculated ones. It follows unambiguously from the spectral data that the ground state is the Γ(1)?+?Γ(2) quasi-doublet of the local D(3) point symmetry group for Tb(3+) in the R32 high-temperature structure. The CF calculations revealed the CF parameters and wavefunctions for Tb(3+) in TbFe(3)(BO(3))(4). The value of the Tb-Fe exchange integral and of the effective magnetic field created by the ordered Fe subsystem were estimated as J(fd)?=?0.26?K and B(eff)?=?3.92?T, using the observed splitting Δ?=?32?cm(-1) of the Tb(3+) ground quasi-doublet at the temperature 5?K. The reliability of the obtained parameters was proven by modeling the literature data on the magnetic susceptibility of TbFe(3)(BO(3))(4). Lattice distortions below T(S) were evidenced by the observed changes of probabilities of the forced electric dipole transitions of Tb(3+).     

Strong magnetic instability in correlated metallic Bi(2)Ir(2)O(7)

We report an experimental/theoretical study of single-crystal Bi(2)Ir(2)O(7) that possesses a metallic state with strongly exchange-enhanced paramagnetism. The ground state of Bi(2)Ir(2)O(7) is characterized by the following features: (1) a divergent low-temperature magnetic susceptibility that indicates no long-range order down to 50?mK; (2) strongly field-dependent coefficients of the low-temperature T and T(3) terms of the specific heat; (3) a conspicuously large Wilson ratio R(W)?≈?53.5; and (4) unusual temperature and field dependences of the Hall resistivity that abruptly change below 80?K, without any clear correlation with the magnetic behavior. All these unconventional properties suggest the existence of an exotic ground state in Bi(2)Ir(2)O(7).     

Single-crystal (57)Fe Q-band ENDOR study of the 4 iron-4 sulfur cluster in its reduced [4Fe-4S](1+) state.

(57)Fe Q-band ENDOR has been used to study the [4Fe-4S](1+) state created by gamma irradiation of single crystals of the synthetic model compound [N(C(2)H(5))(4)](2)[Fe(4)S(4)(SCH(2)C(6)H(5))(4)] enriched in (57)Fe. This compound is an excellent biomimetic model of the active sites of many 4 iron-4 sulfur proteins, enabling detailed and systematic studies of its oxidized [4Fe-4S](3+) and reduced [4Fe-4S](1+) paramagnetic states. Taking advantage of the fact that Q-band ENDOR, in contrast with X-Band ENDOR, allows for a very good separation of the (57)Fe transitions from those of the protons, the complete hyperfine tensors of the four iron atoms for the [4Fe-4S](1+) species has been measured with precision. For each iron atom, the electron orbital and electron spin isotropic contributions have been determined separately. Moreover, it is remarkable that two (57)Fe hyperfine tensors attributed to the ferrous pair of iron atoms are very different. In effect, one tensor presents a much larger anisotropic part and a much smaller isotropic part than those of the other. This difference has been interpreted in terms of a differential electron orbital hyperfine interaction among the two ferrous ions.     

Magnetic ordering in double perovskites R2CoMnO6 (R = Y, Tb) investigated by high resolution neutron spectroscopy

We have investigated low energy nuclear spin excitations in double perovskite compounds R(2)CoMnO(6) (R=Y, Tb) by inelastic neutron scattering with a high resolution back-scattering spectrometer. We observed inelastic signals at about 2.1 μeV for Y(2)CoMnO(6) and also for Tb(2)CoMnO(6) at T = 2 K in both energy-loss and energy-gain sides. We interpret these inelastic peaks to be due to the transitions between the hyperfine split nuclear levels of the (59)Co nucleus. The inelastic peaks move towards the central elastic peak and finally merge with it at the magnetic ordering temperature T(C). The energy of the low energy excitations decreases continuously and becomes zero at T(C) ≈ 75 K for Y(2)CoMnO(6) and T(C) ≈ 100 K for Tb(2)CoMnO(6). For Tb(2)CoMnO(6), which contains magnetic rare earth ions, additional quasielastic scattering due presumably to the fluctuations of large Tb magnetic moments was observed. The present study reveals the magnetic ordering of the Co sublattice. The results of this investigation along with that obtained by us for other compounds indicate the presence of unquenched orbital moments in some of the Co compounds.     

DyNi2Mn—magnetisation and M?ssbauer spectroscopy

The physical properties of DyNi₂Mn doped with ⁵⁷Fe have been investigated by X-ray diffraction, magnetisation (10–300?K) and ⁵⁷Fe M?ssbauer spectroscopy measurements (5–300?K). DyNi₂Mn(⁵⁷Fe) crystallizes in the MgCu₂-type cubic structure (Fd^??3m space group). The ordering temperature is found to be T_C?=?99(2) K, much higher than those of DyNi₂ (～22?K) and DyMn₂ (～35?K). Analyses of isothermal M–H curves and the related Arrott plots confirm that the magnetic phase transition at T_C is second order. The magnetic entropy change around T_C is 4.0?J/kg?K for a magnetic field change of 0?T to 5?T. The spectra above T_C exhibit features consistent with quadrupolar effects while below T_C the spectra exhibit magnetic hyperfine splitting. The Debye temperature for DyNi₂Mn has been determined as θ_D?=?200(20) K from a fit to the variable temperature isomer shift IS(T).     

Charge order superstructure with integer iron valence in Fe(2)OBO(3)

Solution-grown single crystals of Fe(2)OBO(3) were characterized by specific heat, M?ssbauer spectroscopy, and x-ray diffraction. A peak in the specific heat at 340 K indicates the onset of charge order. Evidence for a doubling of the unit cell at low temperature is presented. Combining structural refinement of diffraction data and M?ssbauer spectra, domains with diagonal charge order are established. Bond-valence-sum analysis indicates integer valence states of the Fe ions in the charge ordered phase, suggesting Fe(2)OBO(3) is the clearest example of ionic charge order so far.     

NMR study of the magnetic and metal-insulator transitions in Na0.5CoO2: a nesting scenario

Co and Na NMR are used to probe the local susceptibility and charge state of the two Co sites of the Na-ordered orthorhombic Na(0.5)CoO(2). Above T(N) = 86 K, both sites display a similar T dependence of the spin shift, suggesting that there is no charge segregation into Co(3+) and Co(4+) sites. Below T(N), the magnetic long range commensurate order found is only slightly affected by the metal-insulator transition at T(MIT) = 51 K. Furthermore, the electric field gradient at the Co site does not change at these transitions, indicating the absence of charge ordering. All these observations can be explained by successive spin-density wave induced by two nestings of the Fermi surface specific to the x = 0.5 Na ordering.     

Debye temperature and magnetic ordering in K x Ba1−x Fe2S3

⁵⁷Fe Mössbauer measurements are reported for the series K _x Ba_1?x Fe₂S₃, x ≤ 0.3, at temperatures between 4.2 K ≤ T ≤ 294 K. A decrease of the Debye temperature from 435 to 405 K with x, indicates a weakening of the stiffness of the Fe sublattice. The ordering temperatures, taken from the appearance of magnetic hyperfine splitting in the spectra, are approximately 40 K lower for x ≥ 0.1. The values of the centre shift and the small temperature dependence of the quadrupole splitting strongly supports that similar to the border compound BaFe₂S₃ also the K containing samples should be characterised as mixed valence compounds.     

Magnetism at single isolated iron atoms implanted in graphite

M?ssbauer spectra obtained after implantation of 57Fe into highly oriented pyrolytic graphite (HOPG) show a combined magnetic and quadrupole interaction with a magnetic hyperfine field Bhf = 32.6 T at 14 K. Though magnetic effects in nominally diamagnetic HOPG have been reported recently, no experiment has previously shown the existence of magnetism at the atomic scale. The results suggest that magnetic ordering occurs by coupling of the Fe magnetic moment to structural and/or electronic magnetic defects induced by the probe atoms' implantation damage.     

Determination of fine and hyperfine structure in Fe−Mo(W) dinuclear clusters

The fine and hyperfine structure of two dinuclear sulfide bridged Fe?Mo complex anions and their W homologues have been studied by magnetic susceptibility and Mössbauer measurements. It is shown that, by following a stepwise methodology, it is possible to derive from the low temperature magnetization data the value and sign of the fine structure parametersD andE/D. These parameters are further confirmed by an independent analysis of the Mössbauer data. Magnetic and electric hyperfine interaction parameters are also determined from the Mössbauer results. Both fine and hyperfine parameters point to a valence scheme, for all complexes, of Fe^II?Mo^VI(W^VI) with a varying degree of charge delocalization from the iron to the molybdenum (tungsten) site. The parameterD is negative with an orientation of itsz axis close to theV _zz axis.     

Resolved magnetic hyperfine spectra of Au-Fe alloys as a function of temperature

We have analyzed the Mössbauer hyperfine magnetic spectra of six compositions of Au-Fe from 10.5 to 33 at.% Fe at temperatures ranging from 4.2 K to the magnetic ordering temperature of each alloy. Only two elementary magnetic hyperfine spectra are required to fit the data, each of which has its own value of the magnetic hyperfine field, quadrupole coupling, isomer shift, and relative intensities. The intensity ratios of the two spectra for a given Fe concentration are essentially invariant with temperature. These results point to the existence of two chemically different Fe sites with all the Fe atoms magnetically coupled over the entire temperature regime below the upper magnetic ordering temperature. A relatively sharp increase in the local moment commences at both Fe sites, at ∼ 17 at.% Fe and continues to increase with Fe concentration.     

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.     

First-principles studies of the magnetic hyperfine field in Fe multilayers

A detailed theoretical study of the magnetic moments and magnetic hyperfine fields in several Fe multilayers (Fe fcc(001)/5X fcc(001), X=Cu and Ag, and Fe bcc(001)/5X fcc(001), X=Ag and Au) as well as in bulk Fe is presented. The calculations have been performed using the spin-polarized, relativistic linear muffin-tin orbital (SPR-LMTO) method of band structure calculation. Therefore, not only the contribution to the hyperfine fields due to the conventional Fermi contact interaction but also due to the spin dipolar and orbital contributions induced by the crystal field and by spin-orbit coupling are accounted for. To decompose the hyperfine field of non-s-electrons into these contributions it has been assumed that they are proportional to the corresponding so-called magnetic dipole moment and the orbital magnetic moment, respectively. In contrast to previous results for pure metals and alloys not only the orbital but also the spin dipolar hyperfine field was found to be non-negligible. The anisotropy of the hyperfine field determined by calculations for in-plane and perpendicular orientation of the magnetisation was found to be very pronounced and closely connected with the corresponding anisotropy of the magnetic dipole moment and the orbital moment.