Ilvaite: A study of temperature dependent electron delocalization by the mössbauer effect

The mixed valence iron silicate ilvaite, CaFe ₂ ²⁺ Fe³⁺Si₂O₈(OH), displays electron delocalization associated with Fe²⁺→Fe³⁺ charge transfer as observed by Mössbauer spectroscopy. Previous studies report the observation of an ‘electron hopping phenomenon’ with resolution of discrete valence states below 320 K. Mössbauer spectra of a suite of naturally occurring ilvaites were recorded over a temperature range, 80 K to 575 K. Five quadrupole doublets were resolved by computer fitting and assigned to Fe²⁺(A), Fe²⁺(B), Fe³⁺(A), and Fe²⁺(A)→Fe³⁺(A)‖c and ⊥c. Contrary to prior work, doublets associated with electron delocalization are resolved at 80 K and preclude the use of a Verwey-type order-disorder model. We propose a thermal activation model and discuss its criteria from molecular orbital and mineralogical viewpoints.     

Electron delocalization and magnetic behavior in a single crystal of ilvaite,a mixed valence iron silicate

Ilvaite, Ca(Fe²⁺, Fe³⁺)Fe²⁺Si₂O₈(OH), a black mixed valence iron silicate shows considerable Fe²⁺?Fe³⁺ electron delocalization above 400 K, reminiscent of magnetite. A crystallographic phase transition from orthorhombic (Pnam) to monoclinic (P2 ₁/a) symmetry takes place on cooling at 343 K induced by electron ordering. In both phases, Fe²⁺ and Fe³⁺ occur in double octahedral chains parallel to the c axis. The thermal characteristics of the magnetic susceptibilities and their anisotropies in different crystallographic planes have been measured in the temperature range 400?21 K. Below 343±1K, a continuous rotation of the molar susceptibility K _∥ in the ab plane down to 90±2 K is observed, where the symmetry of the magnetic ellipsoid remains unchanged. X _a, X _b and X _c increase abruptly below 123±0.5 K, although antiferromagnetic ordering of Fe²⁺ and Fe³⁺ spins on A sites was suggested in previous Mössbauer and neutron powder diffraction studies. In addition, 1/X _a shows an antiferromagnetic maximum at 50±3 K, whereas 1/X _b and 1/X _c at first increase sharply below 123 K, followed by antiferromagnetic curvatures in the lowest temperature region. This behavior is consistent with the antiferromagnetic ordering of Fe²⁺ spins in the B sites. The observed magnetic phenomena suggest charge delocatization effects between adjacent Fe²⁺(A)-Fe³⁺(A) pairs not only along c, but also along a and b directions. The negative sign of the molar anisotropy (K _∥-K_⊥) suggests a singlet ground State ⁵A₁ for the Fe²⁺ ions, in agreement with previous Mössbauer studies.     

Electron delocalization in ilvaite,a reinterpretation of its 57Fe Mössbauer spectrum

The Mössbauer spectra of ilvaite CaFe ₂ ²⁺ Fe³⁺[Si₂O₇/O/OH] and their temperature dependence between 298 K and 455 K can be satisfactorily least-squares fitted by a superposition of the resonances for Fe²⁺(8d), Fe³⁺(8d) and Fe²⁺(4c). The relative areas under the three resonances are nearly equal and vary only weakly with temperature. No additional resonances or line broadenings have to be introduced, if we assume that the hyperfine interactions of Fe²⁺(8d) and Fe³⁺(8d) fluctuate between their values due to electron hopping between the iron ions at the 8d sites. Hopping can be assumed to occur homogeneously among nearly equivalent sites. The fluctuation rate is described by an Arrhenius law with a pre-exponent of about 9 × 10⁸ s^?1 and an activation energy of 0.11 eV indicating non-adiabatic hopping. In addition to the intersite hopping process, the strong decrease of the quadrupole splitting and the isomer shift of Fe²⁺(8d) between 298 K and 360 K suggests the occurrence of intrinsic charge delocalization from Fe²⁺(8d) which does not involve the neighbouring Fe³⁺(8d) ions.     

Molecular orbital (SCF-Xα-SW) theory of metal-metal charge transfer processes in minerals

A number of mixed valence iron oxides and silicates (e.g., magnetite, ilvaite) exhibit thermally induced electron delocalization between adjacent Fe²⁺ and Fe³⁺ ions and optically induced electronic transitions which are assigned to Fe²⁺→Fe³⁺ intervalence charge transfer. In this paper, the mechanism of electron delocalization (i.e., polarons versus itinerant electrons) and the nature of optically induced intervalence charge-transfer in minerals are investigated using molecular orbital theory. SCF-Xα-SW molecular orbital calculations were done for several mixed-valence (Fe₂O₁₀)^15? clusters corresponding to edgesharing Fe²⁺ and Fe³⁺ coordination polyhedra. A spinunrestricted formalism was used so that the effect of ferromagnetic versus antiferromagnetic coupling of adjacent Fe²⁺ and Fe³⁺ cations could be determined. The molecular orbital results can be related to the polaron theory of solid state physics and the perturbation theory formalism used by Robin and Day (1967) and others to describe electron transfer in mixed valence compounds. Intervalence charge-transfer results from the overlap of Fe(3d) orbitals across the shared edges of adjacent FeO₆ polyhedra to give weak Fe-Fe bonds. Electron delocalization, however, requires that adjacent Fe cations be ferromagnetically coupled. Antiferromagnetic coupling results in distinguishable Fe²⁺ and Fe³⁺ cations. Electronic transitions between the Fe-Fe bonding and Fe-Fe antibonding orbitals results in the optically-induced intervalence charge transfer bands observed in the electronic spectra of mixed valence minerals. Such transitions are predicted to be polarized along the metal-metal bond direction, in agreement with experimental observations.     

Crystal chemistry of ferric iron in (Mg,Fe)(Si,Al)O<Subscript>3</Subscript> majorite with implications for the transition zone

Fifteen samples of (Mg,Fe)SiO₃ majorite with varying Fe/Mg composition and one sample of (Mg,Fe)(Si,Al)O₃ majorite were synthesized at high pressure and temperature under different conditions of oxygen fugacity using a multianvil press, and examined ex situ using X-ray diffraction and Mössbauer and optical absorption spectroscopy. The relative concentration of Fe³⁺ increases both with total iron content and increasing oxygen fugacity, but not with Al concentration. Optical absorption spectra indicate the presence of Fe²⁺–Fe³⁺ charge transfer, where band intensity increases with increasing Fe³⁺ concentration. Mössbauer data were used in conjunction with electron microprobe analyses to determine the site distribution of all cations. Both Al and Fe³⁺ substitute on the octahedral site, and charge balance occurs through the removal of Si. The degree of Mg/Si ordering on the octahedral sites in (Mg,Fe)SiO₃ majorite, which affects both the c/a ratio and the unit cell volume, is influenced by the thermal history of the sample. The Fe³⁺ concentration of (Mg,Fe)(Si,Al)O₃ majorite in the mantle will reflect prevailing redox conditions, which are believed to be relatively reducing in the transition zone. Exchange of material across the transition boundary to (Mg,Fe) (Si,Al)O₃ perovskite would then require a mechanism to oxidize sufficient iron to satisfy crystal-chemical requirements of the lower-mantle perovskite phase.     

Mössbauer spectra of kyanite,aquamarine, and cordierite showing intervalence charge transfer

The blue colors of several minerals and gems, including aquamarine (beryl, Be₃Al₂Si₆O₁₈) and cordierite (Al₃(Mg, Fe)₂Si₅AlO₁₈), have been attributed to charge transfer (CT) between adjacent Fe²⁺ and Fe³⁺ cations, while Fe²⁺→Ti⁴⁺ CT has been proposed for blue kyanites (Al₂SiO₅). Such assignments were based on chemical analyses and on polarization-dependent absorption bands measured in visible-region spectra. We have attempted to characterize the Fe cations in each of these minerals by Mössbauer spectroscopy (MS). In blue kyanites, significant amounts of both Fe²⁺ and Fe³⁺ were detected with MS, indicating that Fe²⁺→Fe³⁺ CT, Fe²⁺→Ti⁴⁺ CT, and Fe²⁺ and Fe³⁺ crystal field transitions each could contribute to the electronic spectra. In aquamarines, coexisting Fe²⁺ and Fe³⁺ ions were resolved by MS, supporting our assignment of the broad, relatively weak band at 16,100 cm^?1 in E∥c spectra to Fe²⁺→Fe³⁺ CT between Fe cations replacing Al³⁺ ions 4.6Å apart along c. A band at 17,500 cm^?1 in E⊥c spectra of cordierite is generally assigned to Fe²⁺ (oct)→Fe³⁺ (tet) CT between cations only 2.74 Å apart. However, no Fe³⁺ ions were detected in the MS at 293K of several blue cordierites showing the 17,500 cm^?1 band and reported to contain Fe³⁺. A quadrupole doublet with parameters consistent with tetrahedral Fe³⁺ appears in 77K MS, but the Fe³⁺/Fe²⁺ ratios from MS are much smaller than values from chemical analysis. These results sound a cautionary note when correlating Mössbauer and chemically determined Fe³⁺/Fe²⁺ ratios for minerals exhibiting Fe²⁺→Fe³⁺ CT.     

Fe2+-Fe3+ interactions in tourmaline

The color and spectroscopic properties of ironbearing tourmalines (elbaite, dravite, uvite, schorl) do not vary smoothly with iron concentration. Such behavior has often been ascribed to intervalence charge transfer between Fe²⁺ and Fe³⁺ which produces a new, intense absorption band in the visible portion of the spectrum. In the case of tourmaline, an entirely different manifestation of the interaction between Fe²⁺ and Fe³⁺ occurs in which the Fe²⁺ bands are intensified without an intense, new absorption band. At low iron concentrations, the intensity of light absorption from Fe²⁺ is about the same for E∥c and E⊥c polarizations, but at high iron concentrations, the intensity of the E⊥c polarization increases more than ten times as much as E∥c. This difference is related to intensification of Fe²⁺ absorption by adjacent Fe³⁺. Extrapolations indicate that pairs of Fe²⁺-Fe³⁺ have Fe²⁺ absorption intensity ～200 times as great as isolated Fe²⁺. Enhanced Fe²⁺ absorption bands are recognized in tourmaline by their intensity increase at 78 K of up to 50%. Enhancement of Fe²⁺ absorption intensity provides a severe limitration on the accuracy of determinations of Fe²⁺ concentration and site occupancy by optical spectroscopic methods. Details of the assignment of tourmaline spectra in the optical region are reconsidered.     

Crystallographic phase transition and valence fluctuation in synthetic mn-bearing ilvaite CaFe2+ 2-x Mn2+ xFe3+ [Si2O7/O/(OH)]

The dependence of the electronic and the crystallographic structure on temperature of synthetic Mnbearing ilvaites CaFe²⁺ _2-xMn²⁺ _xFe³⁺ [Si₂O₇/O/OH] with 0≤x≤0.19 has been investigated. The change of the electronic structure was studied by ⁵⁷Fe Mössbauer spectroscopy. The spectra show an increasing valence fluctuation rate between Fe²⁺ and Fe³⁺ in the double chain of edge-sharing octahedra with increasing temperature resulting in a mixed valent state of iron. The valence fluctuation rate is distinctly increased by the Mnsubstitution. The temperature of the crystallographic phase transition T _x as studied by a high temperature Guinier method is distinctly lowered by the Mn-substitution (x = 0.0, T _x=390K; x = 0.12, T _x =370K; x = 0.19, T _x=295K). The reasons for this behaviour are discussed in terms of Fe^{2 +}, Fe^{3 +} cation order-disorder, electronic relaxation rate, and relaxation of the lattice. In the monoclinic phase there is electron hopping between Fe^{2 +}, Fe^{3 +} pairs whereas in the orthorhombic phase there is extended electron delocalization via a narrow, d-band mechanism.     

A dynamical model for the P1 — I1 phase transition in anorthite,CaAl2Si2O8

Electron diffraction and electron microscopic evidence is presented for a dynamical and reversible phase transition in anorthite at T _c=516 K. Antiphase boundaries with a displacement vector, R=1/2[111] become unstable at T _c, while other antiphase boundary loops with the same displacement vector are formed. These interfaces are very mobile and vibrate with a frequency which increases strongly with temperature. At temperatures considerably above T _c, a shimmering effect is observed on imaging in dark field using diffuse c reflections. These observations are in agreement with the interpretation of the high temperature body-centered phase as a statistical dynamical average of very small c type antiphase domains of primitive anorthite. We propose that the c type antiphase domains in primitive anorthite originate from ordered and anti-ordered configurations around Ca²⁺ ions at (ooo) and (oio) [likewise (zoo) and (zio)] positions. The dynamical model for the transition involves a two-stage mechanism: a softmode mechanism causing the aluminosilicate framework to approach body-centered symmetry, followed by an orderdisorder of the Ca²⁺ ion configurations. Close to T _c, statistical fluctuations set in and breathing motion type lattice vibrations of the aluminosilicate framework cause the configurations around Ca (ooo) and Ca(oio) [likewise Ca(zoo) and Ca(zio)] in the configuration to dynamically interchange through an intermediate configuration. The dynamical nature of the phase transition in anorthite is comparable to the — phase transition in quartz.     

Mössbauer study of a California desert celadonite and its pedogenically-related smectite

Celadonite from the northwestern Mojave Desert area of California was examined by detailed Mössbauer spectroscopy at temperatures from 10 K to 400 K. In addition to the predominant Fe³⁺ doublet with isomer shift 0.4 mm s^–1 and quadrupole splitting 0.4 mm s^–1, another Fe³⁺ doublet with 0.4, 1.2 mm/s and two Fe²⁺ doublets with 1.1, 1.7, 2.7 mm s^–1 at 300 K were distinguished. The minor Fe³⁺ component is ascribed to dehydroxylated surface sites. Most of the remaining Fe(90%) is M2 cis-OH octahedral in an ordered M⁺–M²⁺ array. However, about 10% is M1 trans-OH Fe²⁺. Isomer shift vs. T gives Debye temperatures of 570 K for Fe³⁺ in M2 and 380 K for both Fe²⁺ sites, indicating greater vibrational freedom for Fe²⁺. Quadrupole splitting vs. T for Fe²⁺ gives a valence electronic energy splitting of 760 cm^–1 between the ground and first excited state for M2. The M1 sites have a more drastic variation in vs. T which indicates not only a lower first excited state but a rhombic distortion at these sites. A proposed explanation is a neighboring M2 site vacancy. The soil clay formed from this celadonite, which is mostly Fe-rich smectite, was also studied by Mössbauer spectroscopy. About half the Fe²⁺ has been oxidized in the clay, but the isomer shifts and quadrupole splittings are essentially the same as in the original celadonite. A texture orientation in the clay absorber was detected by measuring the absorber at 55° to the source radiation. This texture effect produces asymmetric doublets in the usual 90° measurement.     

A neutron powder diffraction study of the crystal and magnetic structures of ilvaite from 305 K to 5 K — a mixed valence iron silicate with an electronic transition

The crystal and magnetic structures of ilvaite Ca(Fe²⁺, Fe³⁺)Fe²⁺Si₂O₇O(OH) have been obtained by profile refinement of high resolution neutron powder data from a natural sample from Seriphos, Greece. Below about 400 K an electronic transition from an itinerant to an ordered state is expected, with the structure changing from orthorhombic to monoclinic. The structure remains monoclinic P2 ₁/a down to 5 K, with Fe²⁺ almost completely ordered on one of the A-sites and Fe³⁺ on the other: the ordering may increase with decreasing temperature. The B-site contains Fe²⁺ plus a small amount of Mn²⁺ impurity. There are two magnetic transitions, at 116 K and 40 K: at 80 K the Fe²⁺ and Fe³⁺ spins on the A-sites along one infinite c-axis chain are parallel, and antiparallel to those along the adjoined edge-sharing centrosymmetrically related chain. The spin vectors are all perpendicular to the plane of these chains, i.e. almost parallel to the crystallographic b-axis. At 5 K, this order is maintained, but the Fe²⁺ spins on the B-sites order antiferromagnetically as well, again almost along the b-axis. These results explain the earlier Mössbauer and magnetisation measurements.     

Phase transitions in ilvaite,a mixed-valence iron silicate I. A 57Fe Mössbauer study of magnetic order and spin frustration

Ilvaite, Ca(Fe²⁺,Fe³⁺)Fe²⁺Si₂O₈(OH) shows two magnetic phase transitions, which have been studied by Mössbauer spectroscopy within the temperature range 120–4 K. The continued charge localization between Fe²⁺ and Fe³⁺ ions in octahedral A-sites causes the Fe²⁺-Fe³⁺ interaction to be ferromagnetic, although the overall magnetic order is antiferromagnetic. The thermal evolution of the hyperfine fields at the Fe²⁺ (A) and Fe³⁺ (A) sites indicates B _hf: 328 and 523 kOe respectively at 0 K and T _N1= 116K. The corresponding values for Fe²⁺ (B) site are: B _hf 186 kOe and T _N2=36K. An additional hyperfine field exists at the Fe²⁺(B) site within the temperature range 116–36K due to short-range order induced by the spin ordering in A sites. The considerable difference between the two magnetic transition temperatures is due to spin frustration, because the Fe²⁺ (B) site occurs on a corner common between two triangles with respect to two sets of Fe²⁺ (A) and Fe³⁺ (A) sites with opposite spin directions.     

Structure and Mössbauer spectroscopy of barbosalite Fe2+Fe3+ 2 (PO4)2(OH)2 between 80 K and 300 K

Natural barbosalite Fe²⁺Fe³⁺ ₂ (PO₄)₂(OH)₂ from Bull Moose Mine, South Dakota, U.S.A., having ideal composition, was investigated with single crystal X-ray diffraction techniques, Mössbauer spectroscopy and SQUID magnetometry to redetermine crystal structure, valence state of iron and evolution of ⁵⁷Fe Mössbauer parameter and to propose the magnetic structure at low temperatures. At 298?K the title compound is monoclinic, space group P2₁/n, a _o ?= 7.3294(16)?Å, b _o ?=?7.4921(17)?Å, c _o ?=?7.4148 (18)?Å, β?=?118.43(3)°, Z?=?2. No crystallographic phase transition was observed between 298?K and 110?K. Slight discontinuities in the temperature dependence of lattice parameters and bond angles in the range between 150?K and 180?K are ascribed to the magnetic phase transition of the title compound. At 298?K the Mössbauer spectrum of the barbosalite shows two paramagnetic components, typical for Fe²⁺ and Fe³⁺ in octahedral coordination; the area ratio Fe³⁺/Fe²⁺ is exactly two, corresponding to the ideal value. Both the Fe²⁺ and the Fe³⁺ sublattice order magnetically below 173?K and exhibit a fully developed magnetic pattern at 160?K. The electric field gradient at the Fe²⁺ site is distorted from axial symmetry with the direction of the magnetic field nearly perpendicular to V_zz, the main component of the electric field gradient. The temperature dependent magnetic susceptibility exhibits strong antiferromagnetic ordering within the corner-sharing Fe³⁺-chains parallel to [101], whereas ferromagnetic coupling is assumed within the face-sharing [1?1?0] and [?1?1?0] Fe³⁺-Fe²⁺-Fe³⁺ trimer, connecting the Fe³⁺-chains to each other.     

Thermodynamic properties of hematite — ilmenite — geikielite solid solutions

A solution model is developed for rhombohedral oxide solid solutions having compositions within the ternary system ilmenite [(Fe ₂₊ ^s Ti ₄₊ ^1–s ) ^A (Fe ₂₊ ^1–s Ti ₄₊ ^s ) ^B O₃]-geikielite [(Mg ₂₊ ^t Ti ₄₊ ^1–t ) ^A (Mg ₂₊ ^1–t Ti ₄₊ ^t ) ^B O₃]-hematite [(Fe³⁺) ^A (Fe³⁺) ^B O₃]. The model incorporates an expression for the configurational entropy of solution, which accounts for varying degrees of structural long-range order (0s, t1) and utilizes simple regular solution theory to characterize the excess Gibbs free energy of mixing within the five-dimensional composition-ordering space. The 13 model parameters are calibrated from available data on: (1) the degree of long-range order and the composition-temperature dependence of the transition along the ilmenite-hematite binary join; (2) the compositions of coexisting olivine and rhombohedral oxide solid solutions close to the Mg–Fe²⁺ join; (3) the shape of the miscibility gap along the ilmenite-hematite join; (4) the compositions of coexisting spinel and rhombohedral oxide solid solutions along the Fe²⁺–Fe³⁺ join. In the course of calibration, estimates are obtained for the reference state enthalpy of formation of ulvöspinel and stoichiometric hematite (–1488.5 and –822.0 kJ/mol at 298 K and 1 bar, respectively). The model involves no excess entropies of mixing nor does it incorporate ternary interaction parameters. The formulation fits the available data and represents an internally consistent energetic model when used in conjuction with the standard state thermodynamic data set of Berman (1988) and the solution theory for orthopyroxenes, olivines and Fe–Mg titanomagnetite-aluminate-chromate spinels developed by Sack and Ghiorso (1989, 1990a, b). Calculated activity-composition relations for the end-members of the series, demonstrate the substantial degree of nonideality associated with interactions between the ordered and disordered structures and the dominant influence of the miscibility gap across much of the ternary system. The predicted shape of the miscibility gap, and the orientation of tie-lines relating the compositions of coexisting phases, display the effects of coupling between the excess enthalpy of solution and the degree of long-range order. One limb of the miscibility gap follows the composititiontemperature surface corresponding to the ternary second-order transition.     

57Fe Mössbauer spectroscopy and magnetization of cation-deficient Fe2TiO4 and FeCr2O4. Part I:57Fe Mössbauer spectroscopy

⁵⁷Fe Mössbauer spectra are presented for synthetic cation-deficient Fe₂TiO₄ and FeCr₂O₄ spinel particles (<1μm) at various temperatures. The spectra of ferrimagnetic cation-deficient Fe₂TiO₄ show characteristic features due to relaxation because of superparamagnetism and spin relaxation in the temperature range 5–294 K. At 5 K and 78 K, a superposition of at least two sextets is observed which appear to arise from Fe³⁺ onA-sites (Fe _A ³⁺ andB-sites (Fe _B ³⁺ ) of the spinal lattice with magnetic hyperfine fields at 5 K ofB _hf ((Fe _B ³⁺ )≈47.5 T andB _hf (Fe _B ³⁺ )≈51.0 T, respectively. Cation-deficient FeCr₂O₄ particles reveal at 78 K a fieldB _hf (Fe³⁺)≈46.9 T and exhibit relaxation spectra as a consequence of superparamagnetism in the temperature range 80 K - ～300 K. At 294 K, quadrupole splitting Δ(Fe _A ³⁺ )=0.92 mm/s and isomer shift δ(Fe _A ³⁺ )=0.29 mm/s (relative to metallic Fe) are measured. For both compounds the magnetic hyperfine fieldsB _hf are discussed in terms of supertransferred hyperfine fields involving vacancies and in the case of cation-deficient Fe₂TiO₄ also diamagnetic Ti⁴⁺ neighbours of the Fe ions.     

Effects of Fe/Mg on the compressibility of synthetic wadsleyite: β-(Mg1-xFex)2SiO4 (x≤0.25)

Four crystals of synthetic wadsleyite, -(Mg,Fe)₂SiO₄, were mounted together in one diamond-anvil cell for the determination of unit-cell parameters as a function of pressure. The Fe/(Fe+Mg) are 0.00, 0.08, 0.16, and 0.25 (the most iron-rich stable composition). Unit-cell refinements were made at 12 pressures up to 4.5 GPa. No phase transitions were observed and all crystals remained dimensionally orthorhombic. Of the three axes, c is the most compressible (0.000239(3) GPa^-1), whereas compressibilities of a and b are both about 30% less. The Fe content has no systematic effect on volume or linear compressibilities. Bulk moduli, based on a Birch-Murnaghan equation of state (K assumed to be 4.00) are 160(3), 169(3), 164(2), and 165(3) GPa for the four crystals in order of increasing Fe. Substitution of Fe for Mg, therefore, does not appear to have a systematic effect on bulk modulus. Other factors, especially Fe³⁺/Fe²⁺ and other deviations from the strict Mg₂SiO₄-Fe₂SiO₄ binary, may have a greater influence on compressibility.     

Mixed valence of iron in minerals with cation clusters

The valence and distribution of iron in vivianite, lazulite, babingtonite, rockbridgeite, acmite, aegirine-augite, hedenbergite, and ilvaite were studied with optical and Mössbauer spectroscopy. Optically activated intervalence charge transfer between Fe²⁺ and Fe³⁺ in neighboring sites through common edges or faces is observed in all these minerals irrespective of the polymerization of the iron-oxygen polyhedra ranging from finite clusters to infinite structural units. However, a distinct decrease occurs in the energy of the corresponding optical absorption band with increasing number of Fe²⁺ and Fe³⁺ ions involved in the charge transfer process. Thermally activated electron delocalization between Fe²⁺ and Fe³⁺ occurs only if Fe²⁺ and Fe³⁺ occupy crystallographically equivalent or geometrically very similar neighboring sites which share common edges to form extended structural units such as the ribbon in ilvaite. If the Fe-O polyhedra form finite clusters of two, three, or four polyhedra (e.g., in vivianite, lazulite, and babingtonite, respectively) no thermally-activated mixed-valence states of iron are observed. In aegirine, extended regions of the M1 chain are statistically occupied by Fe²⁺ and Fe³⁺ giving rise to thermally-activated electron delocalization in addition to the intervalence band in the optical absorption spectrum. The intensity of the optical intervalence absorption has been measured in a number of systems: ? values range from 60 to 210.     

Magnetic order in grunerite,Fe7Si8O22(OH)2A quasi-one dimensional antiferromagnet with a spin canting transition

Magnetization and neutron diffraction measurements have been made on grunerite, Fe₇Si₈O₂₂(OH)₂, a monoclinic double-chain silicate with Fe²⁺ octahedral bands. The mineral orders antiferromagnetically at 47K into a collinear structure with a second transition at 8K to a canted arrangement. The magnetic susceptibility follows a Curie-Weiss Law above 120K, with a paramagnetic Curie temeprature ?_p=67K. Magnetization measurements below 47K indicate a spin-flop or metamagnetic transition in an applied field of about 12KOe. Powder neutron diffraction measurements between 8–45K reveal that all the Fe²⁺ spins within an octahedral band are ferromagnetically coupled parallel to the b axis, with each band antiferromagnetically coupled to neighboring bands. Below 8K Fe²⁺ spins at the M1 and M4 sites are canted away from the b axis, whereas those at the M2 and M3 sites are not significantly affected. The ordered Fe²⁺ moment on the M4 site is substantially lower than those on the other sites, most likely indicating strong covalency effects, i.e. considerable spin transfer to neighboring oxygen atoms.     

The crystal chemistry of ferric iron in Fe0.05Mg0.95SiO3 perovskite as determined by Mössbauer spectroscopy in the temperature range 80–293 K

Mössbauer spectra were recorded at multiple temperatures between 80 and 293 K to study the nature of Fe³⁺ in Fe_0.05Mg_0.95SiO₃ perovskite that had been synthesised in a multianvil press at 1650 °C and 25 GPa at its mimimum stability limit. The Mössbauer data were fitted to a model with quadrupole splitting distributions (Fe²⁺) and Lorentzian lineshapes (Fe³⁺ and Feⁿ⁺). The centre shift data were fitted to a Debye model with the following results: Θ_M (Fe²⁺)=365±52 K and Θ_M (Fe³⁺)=476±96 K. Hyperfine parameter data for Fe³⁺ suggest occupation of the octahedral site only. The average valence seen by the Mössbauer effect in rapid electron exchange that occurs between Fe²⁺ and Fe³⁺ is calculated from the hyperfine parameters to be 2.50±0.07. Correction of area fractions for site-dependent recoil-free fractions gives a value for Fe³⁺/∑Fe of 9.4±1.4%, which is independent of temperature. A perovskite phase of similar composition synthesised in the multianvil press at higher oxygen fugacity gives a value for Fe³⁺/∑Fe of 16±3%, where Fe³⁺ appears to occupy both sites in the perovskite structure.     

Electron relaxation in deerite

The mixed valence iron silicate deerite, Fe ₆ ²⁺ Fe ₃ ³⁺ O₃[Si₆O₁₇](OH)₅ whose crystal structure has only recently been fully determined, had been previously examined by both susceptibility measurements and Mössbauer spectroscopy. We reinterpret the Mössbauer measurements from Frank and Bunbury and show that all contradictions between the phenomena, observed in their experiments, and the mineralogical structure disappear when one accepts a thermally activated electron delocalisation associated with Fe²⁺ ? Fe³⁺ charge transfer.