Influence of the coordination water on the after effects of the K-capture in57Co doped FeSO4×H2O (x=0,1,4,7)

Emission Mössbauer spectroscopy is used to investigate the physico-chemical state of⁵⁷Fe atoms generated by⁵⁷Co²⁺ clectron capture in⁵⁷Co: FeSO₄xH₂O (x=0,1,4,7). The spectra of all the hydrates show at least three main components, the normal bivalent state, Fe²⁺(N), an aliovalent state, Fe³⁺, and one (or several) anomalous ferrous species in which the coordination sphere has been perturbated by the self-radiolysis. No Fe³⁺ is observed in the anhydrous compound whereas the intensity of this component increases as a function of the hydration number, reaching a saturation value of 36% for x=4 and 7.     

Characterisation of synthetic trioctahedral micas by Mössbauer spectroscopy

Trioctahedral potassium micas |K}[M₃]〈T₄〉O₁₀(OH)₂ have been synthesized by hydrothermal techniques with various cationic substitutions in the octahedral and the tetrahedral sheet. Taking annite |K}[Fe ₃ ²⁺ ]〈AlSi₃〉O₁₀(OH)₂ as the reference mineral, [Fe²] was replaced by [Mg²] and [Ni²], 〈Al³⁺〉 by 〈Fe³⁺〉 and finally [Fe²⁺] + 〈Si⁴⁺〉 by [Al³⁺] + 〈Al³⁺〉. Mössbauer spectra were evaluated in terms of quadrupole splitting distributions (QSDs) using three generalized sites for 〈Fe³⁺〉, [Fe³⁺] and [Fe²]. Annites, nominally free of 〈Fe³⁺〉, show a lower limit of [Fe³⁺]/Fe _tot of 0.10, which stabilizes the structure. The ferrous iron, [Fe²], QSD consists of two main components. In some of the solid solution series, there is strong experimental evidence for a third ferrous component, particularly at higher [Al³⁺] contents. This third component is centered at low quadrupole splittings and may be assigned to a defect [Fe²] site, forming 1:2 structures with two neighbouring trivalent octahedral cations. For charge compensation one OH^? is replaced by O^2? for each [M³⁺] cation. The ferrous QSDs vary systematically with chemical composition. Compared to those of annite, the QSD parameters (mean quadrupole splitting 〈QS〉 and quadrupole splitting with maximum probability, QS _peak ) are shifted towards higher values with increasing [Mg²] and [Ni²] contents, and decrease slightly with increasing content of trivalent cations. These trends can be interpreted in terms of changes in the local environment around the Fe probe nucleus, i.e., in terms of decreasing or increasing distortions from the ideal octahedral configurations.     

Ferrous porphyrins with an “unusually” large quadrupole splitting

High-spin ferrous metalloporphyrins Fe^II(NCH₃TPP)Cl, Fe^II(NCH₃TPP)Br, Fe^II(NCH₃TPP)ClO₄, and Fe^II(NCH₃OEP)Cl(NCH₃TPP-N-methyltetraphenylporphyrin, NCH₃OEP-N-methyloctaethylporphyrin) have been characterized by Mössbauer spectroscopy. Values ofIS (0.8 mm/s versus α-Fe) typical for high-spin ferrous porphyrin and very large quadrupole splittings (?4 mm/s) have been observed. Iron(II) N-methylporphyrins should be readily detected in proteins by means of Mössbauer spectroscopy. Such parameters are similar to those of symmetrical anionic five coordinate high-spin porphyrins [Fe^II(TPP)X]^? (X-halide).     

Magnetocrystalline anisotropy and inversion degree of manganese-ferrous-ferrites

Torque measurements have been performed at 4 and 77 K on single crystals of Mn_1?xFe_2+xO₄ (0<x<0.05) and MnFe_2?xTi_xO₄ (0<x<0.1). The crystals were either quenched or slowly cooled causing a change of inversion by 0.1. It is found that the magnetic anisotropy due to the ferrous ions in the Ti-doped samples is 80 per cent larger than in the Mn_1?xFe_2+xO₄ crystals. In both crystal series the ferrous ion anisotropy in the slowly cooled crystals is 70 per cent higher than in the quenched crystals. The K₁ of MnFe₂O₄ at 4 K is found to decrease from ?3.6 × 10⁵ erg/cm³ after show cooling, down to ?2.6 × 10⁵ erg/cm³ after quenching.     

Single-Crystal Fe Q-Band ENDOR Study of the 4 Iron–4 Sulfur Cluster in its Reduced [4Fe–4S] State

⁵⁷Fe Q-band ENDOR has been used to study the [4Fe–4S]¹⁺ state created by γ irradiation of single crystals of the synthetic model compound [N(C₂H₅)₄]₂[Fe₄S₄(SCH₂C₆H₅)₄] enriched in ⁵⁷Fe. 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 ⁵⁷Fe 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 ⁵⁷Fe 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.     

Synthesis by Coprecipitation of Al-Substituted Hydroxysulphate Green Rust FeII 4FeIII (2−y)AlIII y (OH)12SO4,nH2O

Al-substituted hydroxysulphate green rust (Al-GR{SO₄}) were synthesised by the coprecipitation of Fe^II, Fe^III and Al^III cations. The Al-GR{SO₄} crystals (～50 nm) are significantly smaller than the hydroxysulphate green rust GR{SO₄} crystals (～500 nm). The Mössbauer spectrum of Al-GR{SO₄} was adjusted with two ferrous doublets D₁ and D₃ and one ferric doublet D₂. Doublet D₃ is attributed to Fe^II ions that have Al^III ions as a first neighbour.

     

The Mössbauer spectrum of synthetic hureaulite: Fe5 2+(H2O)4(PO4H)2(PO4)2

The crystal structure of synthetic ferrous hureaulite, Fe₅ ²⁺ (H₂O)₄(PO₄H)₂(PO₄)₂, was refined from single-crystal X-ray data. It is monoclinic, space group C2/c, with a=17.487(4), b=9.017(2), c=9.338(2) Å, β=96.27(3)°, V=1463.6(6) Å³, Z=4 and D _calc=3.327 g/cm³. This end member of the hureaulite series was crystallized under distinctly acidic conditions, by a method that gives perfect crystals, large enough for X-ray single crystal studies. The main feature of the hureaulite structure is that it has an equal number of normal (PO₄)³⁺ and acid (PO₄H)²⁺ tetradentate groups. These are centered on Fe²⁺ atoms and share corners with edge-linked octahedra, forming pentamer units. The five Fe²⁺ atoms are distributed on three distinct sites in these units. This can be directly observed in the Mössbauer spectrum at 295 K, which contains three doublets whose relative intensities correspond to the 1:2:2 distributions of crystallographic sites.     

Spectroscopic and structural investigations of the ferrous and ferric high-spin state of a “picket—fence” porphyrinato acetato iron complex. A refined model for the P460 center of hydroxylamine oxidoreductase

Mössbauer investigations were performed in the ferrous and ferric form of the ‘picket-fence’ porphyrinato acetato iron complex |Fe(CH₃CO₂) (TP_pivP)|^1?,0 at temperatures varying from 1.5–200K and in fields of 0–6.2T. The ferrous complex has an unusually large quadrupole splitting, ΔE_Q=+4.25mms^?1. The quadrupole splitting in the ferric species, ΔE_Q=+1.1mms^?1, is as normally found in ferric high-spin iron porphyrins. Spin-Hamiltonian analysis of the magnetic spectra yields zero-field parameters D=?0.9mms^?1, E/D=0.33 and magnetic hyperfine parameters A_x,y=?17T, A_z=?13.3T in the ferrous high-spin (S=2) complex, and D=7.5cm^?1, E/D≈0 and A_x,y,z=20T in the ferric high-spin (S=5/2) species.     

High-field Mössbauer spectroscopy on dinuclear iron(II) spin crossover complexes

The dinuclear complex [{Fe(L-N₄Me₂)}₂(BzImCOO)](ClO₄)₂*0.5(CH₃)₂CO has been investigated by Mössbauer spectroscopy carried out in the temperature range from T = 5 K up to T = 190 K with externally applied magnetic fields of up to B = 5 T. By means of a consistent simulation of all experimental data sets within the Spin Hamiltonian formalism, the zero-field splitting and the rhombicity parameter of the ferrous high-spin site could be determined to be D?= 7.2 ± 0.5 cm^???1 and E/D?= 0.1 ± 0.02. The sign of the quadrupole splitting is positive which indicates that the ferrous high-spin site of the dinuclear complex [{Fe(L-N₄Me₂)}₂(BzImCOO)]-(ClO₄)₂*0.5(CH₃)₂CO has an electronic ground state with the d _xy orbital twofold occupied.     

Crystal-field interpretation of the temperature dependence of the57Fe Mössbauer quadrupole splitting in two orthopyroxenes

The temperature dependences of the M2 and the M1 ferrous quadrupole splittings in two orthopyroxenes have been studied. The valence contributions to the EFG were calculated from the Boltzmann averages of the expectation values of the EFG components over the corresponding⁵D levels, while the lattice contributions were obtained from lattice summations. The proper⁵D level schemes were each determined by diagonalization of the full crystal-field Hamiltonian, for which the operator coefficients were calculated so as to take into account the real C₁ symmetry of the FeO ₆ ^10– clusters. The calculations were based on the lattice and the charge data related to ferrosilite.     

Electronic Raman spectra of iron doped MgO

The nearby excited states of Fe²⁺ in MgO are investigated by Raman spectroscopy. We observed an A_1g impurity mode (185 cm^?1) and an electronic transition at 110.5 ± 0.8 cm^?1 which we associate with the first excited states of the ferrous ion, Γ₃ and Γ₄, previously observed by far infrared optical absorption.     

Hyperfine interactions and structures of ferrous hydroxide and green rust II in sulfated aqueous media

A sulfated ferrous hydroxide is obtained by mixing NaOH with melanterite depending on the R=[SO₄ ⁻⁻]/[OH⁻] ratio and leading by oxidation to the green rust II transient compound. Hyperfine parameters are presented.     

A study of the cobalt sites in cobalt and iron molybdate catalysts by emission Mössbauer spectroscopy

Molybdates samples containing 74MBq (2mCi) of cobalt 57 have been studied by emission Mössbauer spectroscopy. Spectra of⁵⁷CoMoO₄ exhibited the three usual Fe²⁺ doublets corresponding to α and β ferrous phases, and two Fe³⁺ doublets accounting for about one third of the absorption area. The Co²⁺ sites of β⁵⁷CoMoO₄ phase exhibit higher quadrupole splittings, i.e. are more dissymmetrical than Fe²⁺ sites of βFeMoO₄ phase. Cobalt and iron molybdates Fe_x ⁵⁷Co_1?xMoO₄ provided spectra where only one Fe³⁺ doublet appeared and occupied less than 7% of the spectral area. It is concluded that a part of cobalt was present in⁵⁷CoMoO₄ as Co³⁺.     

Efficiency and purity control in the preparation of pure and/or aluminum-doped barium ferrites by hydrothermal methods using ferrous ions as reactants

The synthesis of hexagonal barium ferrite (BaFe₁₂O₁₉) was studied under hydrothermal conditions by a method in which a significant amount of ferrous chloride was introduced alongside ferric chloride among the starting materials. Though all of the Fe²⁺ ions in the starting material were converted to Fe³⁺ ions in the final product, Fe²⁺ was confirmed to participate differently from the Fe³⁺ used in the conventional method in the mechanism of forming barium ferrite. Indeed the efficiency of the synthesis and the quality of the product and the lack of impurities such as Fe₂O₃ and BaFe₂O₄ were improved when Fe²⁺ was included. However, the amount of ferrous ions that could be included to obtain the desired product was limited with an optimum ratio of 2:8 for FeCl₂/FeCl₃ when only 2 h of reaction time were needed. It was also found that the role of trivalent Fe³⁺ could be successfully replaced by Al³⁺. Up to 50% of the iron could be replaced by Al³⁺ in the reactants to produce Al-doped products. It was also found that the ratio of Fe²⁺/M³⁺ could be increased in the presence of Al³⁺ to produce high quality barium ferrite.     

Monocrystalline high-saturation magnetization ferrites for video recording head application: I. Zn ferrous ferrites

Monocrystalline Zn ferrous ferrites Zn_xFe_3-xO₄, with x ? 0.4, are considered as candidate materials for video recording heads, to be used for writing on magnetic tapes of high coercivity. The saturation magnetization of these ferrites can be as high as 0.7 T at 20°C. We show that because of the small dimensions of modern video recording heads, the relatively high electrical conductivity of the Zn ferrous ferrites is not an obstacle to their use at video frequencies. Measurements are reported of magnetic and electrical parameters relevant to recording head application. It is shown that some of the magnetic parameters can be influenced positively by Co^II additions. The present paper is the first of a series of three dealing with Fe^II-rich ferrites for video recording head application.     

Fe2+ spin transition in [Fe(trz)(Htrz)2](BF4) as evidenced by a variable temperature EPR study

The EPR of Fe³⁺ ions has been used for the first time to evidence a low-spin (S=0) to high-spin (S=2) transition of Fe²⁺ ions in an octahedral ferrous complex [Fe(trz)(Htrz)₂](BF₄). The temperature dependence of the intensity of the Fe³⁺ EPR line atg=4.3 reveals a spin transition which occurs for the Fe²⁺ ions, with hysteresis. The transition temperatures areT _c↑=374 K in the warming mode andT _c↓=345 K in the cooling mode. The analysis of the EPR spectral data indicates the presence of a structural phase transition accompanying the spin transition.     

Site-selective detection of vibrational modes of an iron atom in a trinuclear complex

Nuclear inelastic scattering (NIS) experiments on the trinuclear complex [⁵⁷Fe{L-N₄(CH₂Fc)₂} (CH₃CN)₂](ClO₄)₂ have been performed. The octahedral iron ion in the complex was labelled with ⁵⁷Fe and thereby exclusively the vibrational modes of this iron ion have been detected with NIS. The analysis of nuclear forward scattering (NFS) data yields a ferrous low-spin state for the ⁵⁷Fe labelled iron ion. The simulation of the partial density of states (pDOS) for the octahedral low-spin iron(II) ion of the complex by density functional theory (DFT) calculations is in excellent agreement with the experimental pDOS of the complex determined from the NIS data obtained at 80 K. Thereby it was possible to assign almost each of the experimentally observed NIS bands to the corresponding molecular vibrational modes.     

Rotation–torsion analysis of the Si2H6 infrared fundamental ν9, perturbed by excited torsional levels of the vibrational ground state

The lowest infrared active perpendicular fundamental ν₉ of disilane has been analysed on a Fourier transform spectrum between 320 and 430?cm^?1, at the spectral resolution of 0.0012?cm^?1. The rotation–torsion structure of this band is affected by x,y Coriolis interactions with excited torsional levels of the vibrational ground state, correlating with components of 3ν₄ and 4ν₄ in the high barrier limit. The interaction of ν₉ and 4ν₄, forbidden in the D_3d symmetry limit, is allowed between components of E torsional symmetry under the G₃₆(EM) extended molecular group, because of the large amplitude of the internal rotation motion. We could determine the values of the main vibration–rotation–torsion parameters of ν₉, interaction parameters, and the vibrational wavenumbers of the four torsional components of 3ν₄ and of the E_3d component of 4ν₄. The intrinsic torsional splitting of ν₉ is found to be smaller than in the ground vibrational state by 0.0066?cm^?1, in good agreement with our theoretical predictions. The possibility of observing the effects of D_3d-forbidden interactions in the spectra of ethane-like molecules is also discussed.     

NGR study of iron molybdates and iron-cobalt molybdates catalysts

Iron molybdates FM and cobalt-iron molybdates CF _x M (which means Co_1?y Fe _y MoO₄ withy=x/100 6≤x≤67), used as matrix of catalysts for propene mild oxidation, were studied by Mössbauer spectroscopy at 295 K and 4 K. All the spectra exhibit three Fe²⁺ doublets, two of them correspond to β-FeMoO₄ and the third one to α-FeMoO₄. Enhancement of quadrupole splittings of Fe²⁺ in the spectra of the CF _x M catalysts is ascribed to the occurrence of a solid solution of either iron in CoMoO₄ or cobalt in FeMoO₄. In each spectrum at 295 K one or several Fe³⁺ doublets were present, which low temperature spectra allow to be assigned to Fe₂(MoO₄)₃, small particles of Fe₂O₃, solid solution of Fe³⁺ in ferrous molybdates and even Fe₂MoO₄ in some cases. The behaviour of all the iron species of these solids during reduction by hydrogen is described.     

Raman spectroscopy studies of antiferromagnetic FeCO3 and related carbonates

Raman spectroscopy experiments were performed on antiferromagnetic siderite (natural FeCO₃). Weak lines at room temperature (in addition to the expected vibrational lines) were found to be seven well defined excitations at liquid helium temperature. Polarization tensor components of these new lines were examined at temperatures varying between room and liquid helium temperature. Frequency decreases upon cooling were observed for three of the lines (the greatest change occuring near the Néel temperature, 38 K). By comparison with infrared spectra, variable temperature Raman spectra and impurity analysis of two related crystals (antiferromagnetic MnCO₃ and CaMg(CO₃)₂ containing 6% iron), new explanations for two (741 and 1735 cm^?1) of three previously observed lines and for one (870cm^?1) of the remaining four are presented. The three variable frequency lines (440,1175 and 1225 cm^?1) are considered magnetic excitations between trigonal field, spin-orbit, and exchange split states of the ferrous ion. The frequency decreases upon cooling may be due to unquenched orbital angular momentum resulting in an exchange interaction of a non-Heisenberg form. Symmetry distortion due to magnetic ordering upon cooling may cause the infrared 741 cm^?1 vibration to become Raman-active.