Phase transition with suppression of magnetism in BiFeO<Subscript>3</Subscript> at high pressure

The magnetic behavior of a Bi⁵⁷FeO₃ powdered sample was studied at high pressures by the method of nuclear forward scattering (NFS) of synchrotron radiation. The NFS spectra from ⁵⁷Fe nuclei were recorded at room temperature under high pressures up to 61.4 GPa, which were created in a diamond anvil cell. In the pressure interval 0 < P < 47 GPa, the magnetic hyperfine field H^Fe at the ⁵⁷Fe nuclei increased reaching a value of ～52.5 T at 30 GPa, and then it slightly decreased to ～49.6 T at P = 47 GPa. As the pressure was increased further, the field H^Fe abruptly dropped to zero testifying a transition from the antiferromagnetic to a nonmagnetic state (magnetic collapse). In the pressure interval 47 < P < 61.4 GPa, the value of H^Fe remained zero. The field H^Fe recovered to the low-pressure values during decompression.     

Magnetic collapse and the change of electronic structure of FeBO3 antiferromagnet under high pressure

The effect of high pressures up to 60 GPa on single-crystal and polycrystalline samples of iron borate ⁵⁷FeBO₃ was studied by Mössbauer absorption spectroscopy (⁵⁷Fe nuclei) in a diamond anvil cell. Magnetic field H _hf at the ⁵⁷Fe nuclei increases with pressure but abruptly drops to zero at 46±2 GPa, indicating the crystal transition from the antiferromagnetic to nonmagnetic state. This is accompanied by an abrupt change in the isomer shift and quadrupole splitting. Their values in the high-pressure phase are evidence for the transition of Fe⁺³ ions from a high-spin (S=5/2, ⁶ A _1g ) to low-spin (S=1/2, ⁶ T2g) state (spin crossover). This correlates with an abrupt decrease in the unit-cell volume (by ～9%) and optical gap. The change of the magnetic and electronic structures is explained by Mott’s transition with rupturing of strong d-d-electron correlations.     

Magnetic collapse in yttrium iron garnet Y<Subscript>3</Subscript>Fe<Subscript>5</Subscript>O<Subscript>12</Subscript> at high pressure

The effect of high pressures up to 70 GPa on single-and polycrystalline samples of yttrium iron garnet Y₃⁵⁷Fe₅O₁₂ is studied by Mössbauer absorption spectroscopy (for the ⁵⁷Fe nucleus) in a diamond-anvil cell. It is found that the hyperfine magnetic field H_hf at ⁵⁷Fe nuclei vanishes abruptly at a pressure of 48 ± 2 GPa, which indicates the transition of the crystal from the ferrimagnetic state to nonmagnetic one. The magnetic transition is irreversible. When the pressure decreases, the magnetic state is not recovered and the garnet remains nonmagnetic until zero pressure. The behavior of the quadrupole splitting and isomer shift shows that, simultaneously with the magnetic transition, irreversible electron and possibly spin transitions occur with changes in the local crystalline structure. The mechanisms of the magnetic collapse are discussed.     

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.     

Pressure-induced electron spin transition in the paramagnetic phase of the GdFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> Heisenberg magnet

The HS → LS spin crossover effect (high-spin → low-spin transition) induced by high pressure in the range 45–53 GPa is observed in trivalent Fe³⁺ ions in the paramagnetic phase of a Gd⁵⁷Fe₃(BO₃)₄ gadolinium iron borate crystal. This effect is studied in high-pressure diamond-anvil cells by two experimental methods using synchrotron radiation: nuclear resonant forward scattering (NFS) and Fe K _β high-resolution x-ray emission spectroscopy (XES). The manifestation of the crossover in the paramagnetic phase, which has no order parameter to distinguish between the HS and LS states, correlates with the optical-gap jump and with the insulator-semiconductor transition in the crystal. Based on a theoretical many-electron model, an explanation of this effect at high pressures is proposed.     

57Fe Mössbauer study of SrFeO3 under ultra-high pressure

⁵⁷Fe Mössbauer absorption spectra under ultra-high pressure up to 53 GPa have been measured using a diamond anvil cell for SrFeO_2.97 which is one of the typical Fe⁴⁺ oxides having a cubic perovskite structure. External high pressure up to 53 GPa makes no indication of structural transformation and does not show any change in valence state of iron, however the Néel temperature of 131 K at 0 GP increases to 300 K and the⁵⁷Fe magnetic hyperfine field decreases from 32.9 T at 0 GPa and 6.5 K to 23.3 T at 53 GPa and 300 K.     

Optimization of the conditions of synchrotron Mössbauer experiment for studying electronic transitions at high pressures by the example of (Mg, Fe)O magnesiowustite

The effect of the experimental conditions on the shape of the nuclear resonant forward scattering (NFS) from (Mg_0.75Fe_0.25)O magnesiowustite has been studied at high pressures up to 100 GPa in diamond anvil cells by the method of the NFS of synchrotron radiation from the Fe-57 nuclei at room temperature. The behavior of the system in the electronic transition of the Fe²⁺ ion from the high-spin to low-spin state (spin crossover) near 62 GPa is analyzed as a function of the sample thickness, degree of nonhydrostaticity, and focusing and collimation conditions of a synchrotron beam. It is found that the inclusion of dynamical beats associated with the sample thickness is very important in the approximation of the experimental NFS spectra. It is shown that the electronic transition occurs in a much narrower pressure range (±6 GPa) rather than in a broad range as erroneously follows from experiments with thick samples under strongly nonhydrostatic conditions.     

Terahertz Cyclotron Photoconductivity in a Highly Unbalanced Two-Dimensional Electron–Hole System

The magnetic properties of the α-Fe₂O₃ hematite at a high hydrostatic pressure have been studied by synchrotron Mössbauer spectroscopy (nuclear forward scattering (NFS)) on iron nuclei. Time-domain NFS spectra of hematite have been measured in a diamond anvil cell in the pressure range of 0–72 GPa and the temperature range of 36–300 K in order to study the magnetic properties at a phase transition near a critical pressure of ~50 GPa. In addition, Raman spectra at room temperature have been studied in the pressure range of 0–77 GPa. Neon has been used as a pressure-transmitting medium. The appearance of an intermediate electronic state has been revealed at a pressure of ~48 GPa. This state is probably related to the spin crossover in Fe³⁺ ions at their transition from the high-spin state (HS, S = 5/2) to a low-spin one (LS, S = 1/2). It has been found that the transient pressure range of the HS–LS crossover is extended from 48 to 55 GPa and is almost independent of the temperature. This surprising result differs fundamentally from other cases of the spin crossover in Fe³⁺ ions observed in other crystals based on iron oxides. The transition region of spin crossover appears because of thermal fluctuations between HS and LS states in the critical pressure range and is significantly narrowed at cooling because of the suppression of thermal excitations. The magnetic P–T phase diagram of α-Fe₂O₃ at high pressures and low temperatures in the spin crossover region has been constructed according to the results of measurements.     

Fe-induced magnetic transition in YBa2(Cu1−x 57Fe x )3O6 by NQR and Mössbauer spectroscopy

Nuclear quadrupole resonance spectroscopy (around 30 MHz) on the chain site Cu(1) nuclei in oxygen deficient YBa₂(Cu_1?x Fe _x )₃O₆ doped with different amounts of⁵⁷Fe (x≤0.01) reveal an onset of magnetic order at low temperatures represented by a symmetrical doublet contribution to the nuclear quadrupole resonance (NQR) spectrum. The onset temperatureT _N2 depends on the concentration of Fe reaching 130 K forx=0.01. The splitting forx=0.01 at 100 K corresponds to a net internal field of 0.09 T with a distribution of ≈0.08 T representing about 70 percent of the Cu(1) nuclei.⁵⁷Fe and⁵⁷Co Mössbauer spectroscopy at 4.2 K with and without an external magnetic field of 5 T revealed that belowx=0.00015 Fe spins are decoupled from the Cu(2) moments in the antiferromagnetic state. Results are interpreted in terms of the magnetic model structure suggested by Kadowaki et al. [1].     

High-pressure Mössbauer spectroscopy using synchrotron radiation and radioactive sources

A high-pressure ⁵⁷Fe Mössbauer study of SrFeO₃ up to 74 GPa has been performed with diamond-anvil-cell (DAC) using synchrotron radiation and a radioactive point source of ⁵⁷Co in Rh. SrFeO₃ is known as a typical cubic perovskite with a high-valence state of Fe⁴⁺ and shows metallic conductivity at 0.1 MPa down to 4.2 K. Applying an external high pressure, SrFeO₃ has not shown any structural transformation up to 74 GPa keeping an Fe⁴⁺ state but the Néel temperature increases up to 300 K at 18 GPa. The external high pressure may induce the ferromagnetism in SrFeO₃ by a decrease of the interatomic distance of Fe or an increase of the d-band width. ⁵⁷Fe Mössbauer measurements under externally applied longitudinal magnetic field using radioactive ⁵⁷Co in Rh source and also nuclear forward scattering measurements with a linearly polarized synchrotron radiation under external magnetic field indicate the existence of the pressure induced ferromagnetism in SrFeO₃. In this work we compare high-pressure Mössbauer spectroscopy using synchrotron and radioactive sources and summarize the advantages and disadvantages of each method.     

High-pressure magnetic properties and <Emphasis Type="Italic">P-T</Emphasis> phase diagram of iron borate

The high-pressure magnetic states of iron borate ⁵⁷FeBO₃ single-crystal and powder samples have been investigated in diamond anvil cells by nuclear forward scattering (NFS) of synchrotron radiation at different temperatures. In the low-pressure (0 < P < 46 GPa) antiferromagnetic phase, an increase of the Neél temperature from 350 to 595 K induced by pressure was found. At pressures 46–49 GPa, a transition from the antiferromagnetic to a new magnetic state with a weak magnetic moment (magnetic collapse) was discovered. It is attributed to the electronic transition in Fe³⁺ ions from the high-spin 3d⁵ (S = 5/2, ⁶A_1g) to the low-spin (S = 1/2, ²T_2g) state (spin crossover) due to the insulator-semiconductor-type transition with extensive suppression of strong d-d electron correlations. At low temperatures, NFS spectra of the high-pressure phase indicate magnetic correlations in the low-spin system with a magnetic ordering temperature of about 50 K. A tentative magnetic P-T phase diagram of FeBO₃ is proposed. An important feature of this diagram is the presence of two triple points where magnetic and paramagnetic phases of the high-spin and low-spin states coexist.     

Mössbauer study of CaFeO3 under external high—Pressure

⁵⁷Fe Mössbauer and X-ray diffraction measurements have been performed on a perovskite CaFeO₃ under external high pressure upto 50 GPa at room temperature using a diamond anvil cell. Above 29 GPa the⁵⁷Fe magnetic hyperfine splitting appears superimposing with usual paramagnetic pattern of CaFeO₃. Magnitude of hyperfine field is 16 T and much smaller than 33 T of typical Fe⁴⁺ in SrFeO₃ suggesting a transition from high-spin S=2 to low-spin S=1 state in CaFeO₃.     

Mössbauer spectroscopy in the time domain applied to the study of single‐crystalline guanidinium nitroprusside

Guanidinium nitroprusside GNP, (CN₃H₆)₂[Fe(CN)₅NO] has been investigated in single‐crystalline form by nuclear resonant forward scattering (NFS) using synchrotron radiation (Mössbauer spectroscopy in the time domain). This method provides a direct measure of effective absorber thickness and therefore also of the Lamb–Mössbauer factor f _LM. GNP has the advantage that all [Fe(CN₅)NO]^2- anions are practically aligned within the crystal. For the two different crystal orientations, with the crystallographic a- and c-direction parallel to the synchrotron beam, respectively, we have obtained f _LM ^(a)= 0.122(10) and f _LM ^(c)= 0.206(10), i.e., GNP exhibits significant anisotropic vibrational behavior. The quantum beat pattern of the NFS spectra obtained for the two different crystal orientations is discussed on the basis of radiation characteristics of the polarized synchrotron beam and the multipole transitions of oriented ⁵⁷Fe nuclei.     

Magnetism under high pressure studied by 57Fe and 151Eu nuclear scattering of synchrotron radiation

The nuclear forward scattering (NFS) of synchrotron radiation is especially suited for probing magnetism at very high pressure, here in the Mbar range, by the nuclear resonances of ⁵⁷Fe and ¹⁵¹Eu. We report on high pressure (h.p.) NFS studies with the 14.4 keV transition of ⁵7Fe on magnetic RFe₂ Laves phases of cubic C15 structure (YFe₂, GdFe₂) and hexagonal C14 structure (ScFe₂, TiFe₂) at pressures up to 100 GPa (=1 Mbar). We present also h.p. NFS studies performed with the 21.5 keV resonance of ¹⁵¹Eu, probing the magnetism in the CsCl-type h.p. phase of EuTe. This revised version was published online in August 2006 with corrections to the Cover Date.     

57Fe Mössbauer study of new multiferroic AgFeO2

The present work reports results of the ⁵⁷Fe Mössbauer measurements on AgFeO₂ powder sample recorded at various temperatures including the points of both magnetic phase transitions. The ⁵⁷Fe Mössbauer spectra of AgFeO₂ measured in the paramagnetic range (T > T _N1) consist of one quadrupole doublet with rather high quadrupole splitting of Δ_300K = 0.66 ± 0.01 mm/s for Fe³⁺ ions. In order to predict the sign of electric field gradient (EFG) at ⁵⁷Fe nuclei, we calculated the lattice contribution to the electric field gradient (EFG) at ⁵⁷Fe nuclei, which emphasized the importance of the dipolar contributions, with resultant oxygen polarizabilities in the range of α _O = 0.83 ų, in agreement with the results obtained previously for other delafossite-like oxides. In the temperature range of T _N2 < T < T _N1, Mössbauer spectra gave clear evidence for the existence of a distribution of the hyperfine magnetic fields H _hf at ⁵⁷Fe nuclei. We present the results of a model fitting of the spectra based on an assumption of the cycloid magnetic structure of AgFeO₂ at T < T _N2. The obtained data were analysed in comparison with published data on Mössbauer studies of oxide multiferroics.     

Pressure evolution of the EFG and magnetic hyperfine field in the layered antiferromagnet FeI2

When FeI₂ is subjected to pressures of up to 20 GPa, a change of approximately 20% occurs in the unit cell volume.⁵⁷Fe Mössbauer spectroscopy (MS) in a diamondanvil cell has been used to monitor the pressure evolution of the hyperfine interaction parameters of this layered antiferromagnetic insulator. The pressure dependence of the quadrupole splittingQS at 296 K exhibits a maximum at 12 GPa and the saturation magnetic hyperfine fieldH ₀ increases from 7.4 T at ambient pressure to 12 T at 18 GPa. A qualitative analysis identifies the pressure evolution ofQS with changes in the trigonal component of the crystal field splitting. The pressure variation ofH ₀ is attributed to an increase in the average value of the 3d charge density distribution.     

A Mössbauer effect investigation of the magnetic behaviour of (Fe,Co)S1 + x solid solutions

The Mössbauer spectra of (Fe, Co)S_{1 + x} were recorded at room temperature and 4.2 K for samples of varying composition to study the magnetic behaviour of the solid solutions. The Mössbauer spectra are split magnetically at iron concentrations above 16% Fe. For samples with less than 16%Fe, the Mössbauer spectra show no evidence of magnetic splitting down to 4.2 K. The room temperature centre shift data appear to vary continuously with composition and the hyperfine magnetic field decreases with decreasing Fe²⁺ concentration. A Mössbauer spectrum of ⁵⁷Fe:CoS at 4.2 K in an external field of 25 kOe showed no evidence of magnetic splitting beyond that caused by the applied field, indicating a net zero internal field.A high spin to low spin transition in Fe²⁺ is ruled out as being responsible for the observed magnetic behaviour on the basis of the centre shift data. The Mössbauer data are interpreted to indicate a substantial increase in electron delocalization towards the ligands as the 〈M-S〉 distance decreases with decreasing Fe²⁺concentration. This causes a reduction in the magnitude of the internal magnetic field contributions as well as a decrease of shielding of the nucleus, giving rise to the observed Mössbauer parameters.The Mössbauer spectrum of ⁵⁷Fe:CoS at room temperature is compared with the spectrum of FeS above the 6.7 GPa phase transition at room temperature. The similarities of the centre shift and the 〈M-S〉 distance in the two phases indicate that covalency may also be responsible for the observed high pressure behaviour of FeS, and not the presence of Fe³⁺ as was originally suggested.     

Local magnetic ordering of Fe impurities in Pd2MnSn

Mössbauer effect of Fe⁵⁷ embedded as very dilute substitutional impurities in Pd₂MnSn was studied. The impurities are seen to replace the three elements in the alloy. Although the Curie temperature of the alloy is 189K, well below the room temperature, the Mössbauer spectrum recorded at room temperature consisted of two distinct 6-finger magnetic hyperfine spectra and a single unsplit line. One of the 6-finger patterns which corresponds to an internal magnetic field ofH _int=?375 kOe is inferred to arise due to local magnetic coupling of the localized magnetic moments of Fe impurities at the Pd sites with those of the 4 Mn first nearest neighbours of the Fe impurities. The other 6-finger pattern which corresponds to an internal magnetic field ofH _int=?335 kOe is inferred to arise due to the local magnetic coupling of the localized magnetic moments of the Fe impurities at the Sn sites with those of the 6 Mn second nearest neighboours of the Fe impurities. The difference in the internal magnetic fields observed at the Pd and Sn sites in the alloy could be understood qualitatively, on the basis of RKKY theory, as arising due to the different conduction electron polarization contributions to the net internal magnetic field at the Fe impurity sites. The results of the measurements suggest that the localized magnetic moments of Fe⁵⁷ impurities at Pd and Sn sites are antiferromagnetically coupled with the moments of their neighbouring Mn atoms.     

Relaxation effects in Mössbauer spectra of bridged seven-coordinate Fe3+ pairs

The compound [Fe₂L(H₂O)₄] (ClO₄)₄.H₂O which contains pairs of Fe³⁺ ions within a binucleating macrocycle derived from Schiff base condensation of 2,6-diacetylpyridine and 1,3-diamino-2-hydroxy-propane has been studied by magnetic susceptibility measurements and⁵⁷Fe Mössbauer spectroscopy between 4.2 K and 300 K, and its crystal structure determined. The spectra show relaxation effects at all temperatures. Spectra taken at 4.2 K in applied fields of about 3 T showed thatV _zz is positive and η～0. The spectra were fitted using a stochastic model of a magnetic hyperfine field relaxing parallel to thez axis, giving relaxation times of 10^?9?10^?10 s.     

Mössbauer studies on hyperfine field measurement in titanium doped nickel-zinc ferrites

⁵⁷Fe Mössbauer effect study in the polycrystalline solid solutions of Zn_0.25Ni_{0.75+tTitFe2?2tO4} (t=0.0-0.5) has been carried out at room temperature. All the samples exhibited two pure Zeeman sextets corresponding to tetrahedral and octahedral sites. The present work has been aimed at investigating the influence of tetravalent titanium substitution on the isomer shift, quadrupole splitting, nuclear magnetic fields at ⁵⁷Fe nuclei for tetrahedral and octahedral sites and the cation distribution. The isomer shift was found to be independent of substitution level t. Nuclear magnetic field H_A decreases faster than H_B with t. From the variation of H_A and H_B with t it is concluded that for higher titanium substituted samples, titanium occupies both the B as well as A sites.