Nuclear spin lattice relaxation of191m Ir in Fe

Thermal cycling of the lattice temperature was used to determine the nuclear spin lattice relaxation of^191m IrFe in polarizing fields of 0.05 to 1.3 T. At low temperatures, the relaxation time is not very much shorter than the lifetime of^191m Ir. In the first part of the paper, the master equation formalism is extended to include a finite lifetime. Our result for the reduced relaxation constant, γ² C _K =(1.48±0.11)·10¹⁴ K s^?1 T^?2 (high field limit) is in serious disagreement with that of a spin echo measurement of¹⁹³IrFe, but fits much better into the general systematics. A comparison of relaxation rates for 3d-, 4d-, and 5d-impurities in Fe is given. As a by-product, a Kapitza conductivity constant ofl _K =1.5 mW cm^?2 K^?4±30% was found between Fe and dilute³He/⁴He.     

Ce CORE level X-ray photoelectron spectroscopy of CeX2Si2 (X = Fe,Co, Ni and Cu)

Ce(3d) and (4d) core level XPS spectra of CeX = Fe, Co, Ni and Cu) suggest that the mean valence of Ce was as well as 4f hybridization strength decrease systematically from Fe to Cu. This observation is in agreement with the results of Bremstrahlung Isochromat Spectroscopy (BIS), but in disagreement with L_III-edge data reported earlier.     

Magnetic phase present in YBa2(Cu1−x Fe x )3O6+δ oxides

The Mössbauer study of⁵⁷Fe: YBa₂Cu₃O_6+δ oxides was very important to establish the preferential occupation of Cu(1) site by Fe at very low concentrations. Recent determination of antiferromagnetic ordering for Cu moments in Cu(2) sites (T≈450 K) and our early observation of a small proportion of a magnetic phase at room temperature for Fe:YBa₂Cu₃O₆ lead us to perform systematic studies of YBa₂(Cu_1?x Fe _x )₃O₆ withx=0.005, 0.03, 0.05, 0.10 and 0.15 in order to obtain information about the iron occupation of Cu(2) sites.     

Superconductivity and magnetic order in RBa2Cu3Oz

Mössbauer studies of⁵⁷Fe in RBa_2?y K _y (Cu_1?x Fe _x )₃O_z, with R=Y and Pr;y=0 and 0.5;x=0.01, 0.05 and 0.1 andz between 5.9 and 7.1, have been performed. A minority of the iron ions enter the Cu(2) site and reveal its magnetic order. In nonsuperconducting YBa_1.5K_0.5(Cu_0.95Fe_0.05)₃O_6.1 two distinctly inequivalent magnetic iron sites are observed, probably corresponding to iron in the Cu(2) site with different Ba?K neighbours. In superconducting (T _c =60 K) YBa_1.5K_0.5(Cu_0.95Fe_0.05)₃O_6.5 one Cu(2) subsite remains magnetic (T _N=440 K). The implications of these findings on the valencies of the Cu ions are discussed.     

Effects of Fe2+ and Zn2+ substitution on the structure and high-pressure stability of MgAl2O4 spinel from DFT calculations

Using density functional theory we show the effects of transition (Fe²⁺) and non-transition (Zn²⁺) divalent cationic substitutions on the following structural parameters: lattice parameters, bond lengths and polyhedral volumes under varying hydrostatic pressures. Fe²⁺ and Zn²⁺ substitutions lead to contrasting modifications of tetrahedral Mg–O bond lengths. Fe²⁺ (50%)increase the tetrahedral Mg–O bond lengths by 0.21%, whereas Zn²⁺ (50%) reduce it by 0.06%.We present the equations of state of Mg spinel with 50% Fe and Zn substitutions as a function of pressure. This study presents the decomposition pressure (P_T) of spinel to periclase (MgO) and corundum (α-Al₂O₃) as a function of Fe and Zn concentrations (x). For pure spinel, P_T=12.1 GPa. Fe²⁺substitution lowers P_T linearly with its concentration as P_T=?12.56x+12.02. But, Zn²⁺ increases P_T non-linearly along a quadratic relation: P_T=42.057x²+14.171x+12.174. We calculated the C₄₄ elastic constant to explain the contrasting effects of Fe and Zn on the decomposition pressure of spinel phase.     

Temperature dependent Mössbauer and neutron diffraction studies of Cu x Fe1−x Cr2S4 compounds

The cation distribution and magnetic structure of Cu _x Fe_1?x Cr₂S₄ (x?=?0.1, 0.2, 0.3, 0.4, and 0.5) has been studied by X-ray and neutron diffraction, vibrating sample magnetometer (VSM), and Mössbauer spectroscopy. The charge state of Fe is found to be ferrous (Fe²⁺) for the x?=?0.1 sample; ferric (Fe³⁺) for the x?=?0.5 sample; mixed state (Fe²⁺, Fe³⁺) for the x?=?0.2, 0.3, and 0.4 samples. The Mössbauer spectra of the x?=?0.1 sample show asymmetric line broadening, which is considered to be due to the Jahn–Teller effect of Cu²⁺ ions, and a symmetrical six-line pattern is shown for the x?=?0.5 sample. The valence state of the Cu ions for the x?=?0.1 and 0.5 samples is found to be divalent and monovalent, respectively. The magnetic structure of the samples was determined to be a ferrimagnetic structure with antiparallel alignment of the Fe and Cr ion magnetic moments.     

Theory studies of the local lattice distortions and the EPR parameters for Cu2+, Mn2+ and Fe3+ centres in ZnWO4

The local lattice distortions and the electron paramagnetic resonance (EPR) parameters (g factors, hyperfine structure constants and zero-field splittings) for Cu²⁺, Mn²⁺ and Fe³⁺ in ZnWO₄ are theoretically studied based on the perturbation calculations for rhombically elongated octahedral 3d⁹ and 3d⁵ complexes. The impurity centres on Zn²⁺ sites undergo the local elongations of 0.01, 0.002 and 0.013 Å along the C₂ axis and the planar bond angle variations of 8.1°, 8.0° and 8.6° for Cu²⁺, Mn²⁺ and Fe³⁺, respectively, due to the Jahn–Teller effect and size and charge mismatch. In contrast to the host Zn²⁺ site with obvious axial elongation (～0.31 Å) and perpendicular (angular) rhombic distortion, all the impurity centres demonstrate more regular octahedral due to the above local lattice distortions. The copper centre exhibits significant Jahn–Teller reductions for the spin-orbit coupling and orbital angular momentum interactions, characterised by the Jahn–Teller reduction factor J (≈0.29 ? 1). The calculated EPR parameters agree well with the experimental results. The local structures of the impurity centres are analysed in view of the corresponding lattice distortions.     

Theoretical study of local crystal structure in KZnF3:Fe system

An analysis of the relationship between the EPR trigonal-field parameters and the local crystal structure of KZnF₃:Fe³⁺system is presented by diagonalizing the complete energy matrices for a d⁵ configuration ion in a trigonal crystal field. We propose a two-layer-ligand model, in which the ligands consist of six nearest-neighbor F⁻ ions in the first layer and eight next nearest-neighbor K⁺ ions in the second layer. The calculation indicates that the local structure distortion of KZnF₃:Fe³⁺system is due to the displacement of a K⁺ ion along C₃ axis towards the Fe³⁺ ion, which leads to the shift of the F⁻ ions away from C₃ axis. By simulating the EPR low-symmetry parameters D and (a−F), the distorted angles between the Fe³⁺-F⁻ bonds and C₃ axis are determined, Δθ₁=2.58°, Δθ₂=−1.4° at room temperature (300 K) and Δθ₁=2.84°, Δθ₂=−1.4° at low temperature (77 K). Those results are in good agreement with the experimental findings Δθ₁=2.8±0.3°and Δθ₂=−1.1±0.3°.     

The magnetic hyperfine field at Cu in Fe,Co and Ni and the magnetic moment of the 41 keV, 2+ state of62Cu

The magnetic hyperfine interaction of Cu in Fe, Co and Ni was studied by means of the γ-γ perturbed angular correlation method using⁶²Zn(⁶²Cu) as a probe. With the publishedg-factor (g=+0.661(12)) of the 41 keV, 2⁺ state hyperfine fields ofB _HF=16.95(51) T,B _HF=13.15(41) T andB _HF=4.05(30) T atT=0 K for Cu in Fe, Co and Ni are derived, respectively. The systematic discrepancy of these values with several independent measurements of these hyperfine fields is removed by deriving a new value ofg=0.55(5) for the 41 keV, 2⁺ state of⁶²Cu.     

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].     

Theoretical evaluation of the electron paramagnetic resonance spin Hamiltonian parameters for the impurity displacements for Fe3+ and Ru3+ in corundum

The impurity displacements for Fe³⁺ and Ru³⁺ in corundum (Al₂O₃) are theoretically studied using the perturbation formulas of the spin Hamiltonian parameters (zero-field splitting and anisotropic g factors) for a 3d⁵ (with high spin S = 5/2) and a 4d⁵ (with low spin S = 1/2) ion in trigonal symmetry, respectively. According to the investigations, the nd⁵ (n = 3 and 4) impurity ions may not locate at the ideal Al³⁺ site but undergo axial displacements by about 0.132 Å and 0.170 Å for Fe³⁺ and Ru³⁺, respectively, away from the center of the ligand octahedron along the C₃ axis. The calculated spin Hamiltonian parameters based on the above axial displacements show good agreement with the observed values. The validity of the results is discussed.     

Iron ions in ZSM-5 zeolite: Fe3+ in framework, Fe2+ in extra-framework positions in catalytic N2O decomposition

Fe-ZSM-5 samples containing a combination of ⁵⁷Fe³⁺ in framework (FW) and regular iron in extra-framework (EFW) sites were prepared by introducing ⁵⁷Fe in hydrothermal synthesis, then exchanging Fe²⁺ of natural isotope composition into the lattice. The stability for one part of Fe²⁺ and Fe²⁺ ? Fe³⁺ reversibility for the other part in catalytic decomposition of N₂O is demonstrated by in situ Mössbaer measurements. Formation of dinuclear Fe_FW–O–Fe_EFW pairs is not prevailing.     

Superparamagnetic amorphous Fe1−x C x alloy particles in a ferrofluid

A ferrofluid with ultrasmall magnetic particles (d?3.3 nm) of amorphous Fe_1?x C _x has been studied by Mössbauer spectroscopy and electron microscopy. The values of the particle size estimated by the two methods are in good agreement. The magnetic anisotropy energy constant,K=(1.0±0.3)×10⁵ J m^?3 has been estimated.     

57Fe Mössbauer spectroscopy studies of Sr2Fe1−x Cr x Mo1−x W x O6 double perovskite compounds

Polycrystalline double perovskites Sr₂Fe_1?x Cr _x Mo_1?x W _x O₆ with x = 0, 0.05, 0.10, 0.15, 0.20, and 0.30 have been prepared by sold state reactions. A continuous decrease of the tetragonal unit cell parameters α and c with increasing x values is observed. The highest Curie temperature T _C = 426 K is recorded for the x = 0.10 compound. ⁵⁷Fe Mössbauer spectroscopy measurements indicate a non-integral electronic configuration of ～3d^5.3 for the Fe ions at the ordered double perovskite structure for x ≤ 0.20, which reaches ～3d^5.4 for x = 0.30. Fe–Mo/W anti-site and anti-phase boundary defects are observed in all samples in equal concentrations of around 3% of the total number of Fe ions in their structure.     

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.     

Fragmented 2d 5/2, 1g 7/2 and 1g 9/2 deep proton-hole states of207TI

The three proton-hole states ?2d_5/2, 1g_7/2 and 1g_9/2 are found to be fragmented as a result of coupling of these states with the 3^?, 5^?, 2⁺, 4⁺ and 6⁺ collective states of²⁰⁸Pb. The excited states in²⁰⁸Pb (t,α) reaction can be quantitatively explained in terms of altered 2d_5/2, 1g_7/2 and 1g_9/2 states with the hole-core coupling model.     

Mössbauer study of Fe-substituted orthorhombic and tetragonal YBa2(Cu1-xFex)3O7-σ system

Mössbauer study of orthorhombic and tetragonal YBa₂(Cu_1-xFe_x)₃O_7-σ;x=0.02, 0.04, 0.08 has been done to investigate the two inequivalent Cu-sites. Fe substituting Cu having pyramidal oxygen co-ordination is in Fe³⁺ state while Fe substituting Cu having square planar co-ordination is in Fe³⁺ and Fe⁴⁺ states in dynamic equilibrium.     

Mössbauer studies of magnetic behavior of 3d-doped REBa2Cu3−x Fe x O7+δ (RE=Y,Er, Dy,Gd)

A Mössbauer study has been made on⁵⁷Fe ions substituted into the Cu(1) site of REBa₂Cu_3?x Fe _x O_7+δ (RE=Y, Er, Dy, Gd;x=0.15, 0.30). At low temperature, the iron atoms antiferromagnetically order with a transition temperature which is dependent on the Fe concentration. The temperature dependence of the magnetic subspectra representing Fe ions with various local oxygen environments in YBa₂Cu_3?x Fe _x O_7+δ and ErBa₂Cu_3?x Fe _x O_7+δ fit a 2D-Ising model with a ratio of the anisotropic exchange between the two directions on the order of 0.5–1.0(10^?3) for the Y-compounds and on the order of 1 for the Er-compounds. The magnitude of the local dopant magnetization is related to a short-range chemical order which determines the magnetic chain size and defines the correlation lengths. For the Y-compound, the order is quasi-1D with strong intrachain but very weak interchain coupling. For the Er-compounds, the magnetic coupling is Ising 2D. The strong fluctuation behavior expected in low dimensional systems above and belowT _N is observed via characteristic relaxation in the Mössbauer linewidth nearT _N. For both the Dy- and Gd-compounds, the magnetic order is 3D. The magnitude of the rare-earth magnetic moments appears to affect the character of the magnetic interaction in the Cu(1)-site. However, a Mössbauer effect measurement at¹⁵⁵Gd nuclei in GdBa₂Cu_2.85Fe_0.15O_7+δ (T _N(Fe)～14 K) shows paramagnetic behavior at 4.9 K.     

Two-dimensional spin freezing in Y1−z Ca z Ba2Cu3−x Fe x O7

Hyperfine electric and magnetic interactions in Y_1?z Ca _z Ba₂Cu_3?x Fe _x O_6+y compounds have been studied for different rates of Fe and Ca substitution (x=0.09 and 0.24;z=0.24;y=0?1) by⁵⁷Fe Mössbauer spectroscopy of powder samples obtained by different thermal treatments. Calculations of the Fe³⁺ EFG tensor have been performed for different coordination polyhedra in Cu1 and Cu2 sites. Variations of the direction, amplitude and of the sign of the principal component of the EFG are reported versus the iron displacement from the ideal Cu sites inside the pyramidal and tetrahedral coordination polyhedra. Calculated ΔE _Q and η values are compared with the experimental ones. For the Cu2 site, faithfully probed in both oxygen-depleted and oxygen-saturated samples by fairly large fraction of residing iron atoms, the mutual orientations of the axes of the principal EFG component and that of easiest magnetization are deduced from interrelations between quadrupole parameters for paramagnetic quadrupolar and magnetic Zeeman Mössbauer spectra. In the desoxygenated samples, the coexistence of a long range 2D antiferromagnetic order and of a spin-glass order has been evidenced. For the oxygen-saturated samples, the two-dimensional spin-glass order is observed belowT _f =10 K. The Mössbauer spectra under applied fields at 4.2 K show an easy polarization of the spins in the Cu2 sites.     

The structural significance of the interlayer distances of the layered hybrids (CnH2n+1NH3)2MCl4

Layered perovskite-type hybrids (C_nH_2n+1NH₃)₂MCl₄ are low-dimensional functional materials, of which properties depend both on the specific composition of the inorganic part and on the size of the organic part. Therefore, the hybrids (C_nH_2n+1NH₃)₂MCl₄ (where M=Mn,Fe,Co,Cu,Zn and n=2,4,6,8,10,12) are designed in the following way: M changes the inorganic composition and n changes the size of the organic part. The interlayer distances between the two adjacent inorganic sheets of the hybrids (notated as d) are obtained from their X-ray diffraction patterns. The dependence of the interlayer distances on the carbon atom number, the d–n relations, are established by linear regression method. All the relations between d and n are linear with very high linear dependent coefficients. The hybrids can be divided into two groups according to their d–n relations: the group of M=Mn, Fe, Cu (notated as G1) and the group of M=Co and Zn (notated as G2). The structures are of similarity inside each group but dissimilarity between them. The structural otherness between the two groups comes from their differences of either the inorganic parts or the organic parts. The inorganic frames of G1 are corner-sharing [MCl₆] octahedra but those of G2 are tetrahedra without sharing any geometrical element. It can be deduced that the organic chains have different degrees of interdegitation for different groups of hybrids. These are in agreement with the theoretical calculation of the d values and also supported by the Infrared spectra of the hybrids.