Study of the symmetry of Fe3+ sites in SnO2 by electron paramagnetic resonance

Electron paramagnetic resonance (EPR) of Fe³⁺ in SnO₂ has been realized in a natural single crystal of cassiterite at 9.55 GHz (X-band) and at 34.40 GHz (Q-band). Spectra show the simultaneous presence of four groups of independent signals, each one typical of the immediate environment of a specific paramagnetic iron. Fe³⁺ always substitutes Sn⁴⁺ in an octahedral site. The four paramagnetic centers are due to four different charge compensation mechanisms. The spin Hamiltonian constant values for the SN center and I1 center confirm the former results of the authors about for these two centers. SN and I1 present a weak deviation from axial symmetry. The first preserves the crystallographic local symmetry of the tin site and the second shows a symmetry deviation of 0.6° probably due to the presence of an OH group in the coordination polyhedron. On the other hand, for the Sd1 center and mostly for the Sd2 center, never previously subjected to single crystal EPR measurements, the study of spectra symmetry and the determination of B ₂ ⁰ and B ₂ ² constants produced new data. The Sd1 center could be due to a relaxation of the lattice together with a non local charge compensation mechanism. The Sd2 center presents a strong deviation from axial symmetry with mm local symmetry coordination due to coupling of Fe³⁺ and Nb⁵⁺. This coupling is proven by EPR studies of synthetic cassiterites doped with iron and niobium.     

Optical absorption spectra of iron ions in vivianite

Absorption bands are determined in polarized optical spectra of vivianite Fe₃(PO₄)₂·8H₂O, recorded at room and low temperatures. These bands are caused by spin-allowed d-d transitions in structurally nonequivalent Fe _A ²⁺ (～11000 cm^-1 (γ-polarization) (and) ～12000 cm^-1 (β-polarization)) (and) Fe _B ²⁺ (～8400 cm^-1 (γ, α-polarization) and ～11200 cm^-1 (α-polarization)) ions. A charge transfer band (CTB) Fe _B ²⁺ +Fe _B ³⁺ →Fe _B ²⁺ +Fe _B ²⁺ (～15000 cm^-1) also determined, has polarizing features giving evidence of a change in the Fe _B ²⁺ -Fe _B ³⁺ bond direction, when compared with Fe _B ²⁺ -Fe _B ²⁺ . Bands of exchange-coupled Fe³⁺-Fe³⁺ pairs (～19400, ～20400, ～21300 and ～21700 cm^-1) which appear on oxidation of Fe²⁺ in paired Fe _B octahedra are also characterized.     

Characterization and origin of two Fe3+ EPR spectra in kaolinite

The electron paramagnetic resonance (EPR) spectra of Fe³⁺ in a well cristallized kaolinite from Decazeville in France are well resolved. It is shown that in this sample there are mainly two slightly different spectra, well separated at low temperature and characterized at -150° C by the constants B ₂ ⁰ = 0.112 cm^?1, B ₂ ² = 0.0688 cm^?1 for one and B ₂ ⁰ = 0.116 cm^?1, B ₂ ² = 0.0766 cm^?1 for the second. These two spectra arise from Fe³⁺ substituted for Al³⁺ at the two octahedral positions in equal amounts. The temperature dependence of EPR spectra was studied and was explained by a modification of the octahedral sites.     

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.     

Electron paramagnetic resonance,optical absorption,and magnetic circular dichroism studies of the CO 3 − molecular-ion in irradiated natural beryl

Room temperature X-irradiation of some natural beryls produced several new absorption lines in the electron paramagnetic resonance (EPR) spectrum, a known series of optical absorption lines in the 500–700 nm range, and a shift of the absorption edge to lower energies. Several of the new EPR lines and part of the irradiation-induced shift of the absorption edge disappeared after a few days at room temperature, and were not examined in detail. However, three of the paramagnetic centres responsible for the new EPR lines were stable at room temperature and two of these have previously been identified as atomic hydrogen and the methyl radical, CH₃. These species were stable to ～150 and ～450°C respectively. The third stable species, hitherto unreported, showed a single-line EPR spectrum of axial symmetry, with g∥=2.0051 and g⊥=2.0152. This spectrum was found to be intensity-correlated with the series of optical bands in the 500–700 nm range, after thermal bleaching at 175°C. The EPR and optical spectra are therefore assigned to the same species. It is argued that this species is the CO ₃ ^? molecular ion, located in the widest part of the structural channel and aligned with the plane of the molecule perpendicular to the c axis. The EPR spectrum is consistent with a ² A′₂ ground state of a CO ₃ ^? molecule with trigonal symmetry, and this requires that the optical transition has a ² A′₂ → ² E′ character. Most of the features in the optical spectrum can be assigned to coupling of a totally symmetric mode of frequency ～1020 cm^?1 onto a zero-phonon line at 14,490 cm^?1 and a second weaker line at 16,020 cm^?1. However, both of these two fundamental lines are structured, and the two components show strong temperature-dependent derivative-shaped magnetic circular dichroism (MCD). Furthermore, the overall sign of the MCD for the line at 16,020 cm^?1 is opposite to that at 14,490 cm^?1. The separation (～120 cm^?1) of the two components of the 14,490 cm^?1 line is much larger than that expected from spin-orbit interaction, and the origin of this splitting is not yet understood.     

A study of Gd,Ce and Eu impurities in fluorite deposits by electron paramagnetic resonance and neutron activation analysis

In order to obtain a better understanding of fluorite deposits, rare earth impurities have been analyzed for a large number of samples taken from cross-sections of several low temperature hydrothermal veins. Two types of measurements have been used: Electron Paramagnetic Resonance (EPR) and Neutron Activation Analysis (NAA). For Gd, the ratio of spin concentrations to total concentration [Gd³⁺]/[Gd_total] is close to 1 in all the samples; on the other hand, the ratios [Eu²⁺]/[Eu_total] and [Ce³⁺ -F _? ⁱ ]/[Ce_total] exhibit large variations. The first result suggests that the major part of the lanthanides in the samples is incorporated in the crystal lattice and that clustering of lanthanides ions is not important. The behaviour of Eu and Ce is ascribed to charge state changes and symmetry state changes respectively.     

Electron paramagnetic resonance of PO 3 2− and SO 3 − radicals in anhydrite,celestite and barite: the hyperfine structure and dynamics

Electron paramagnetic resonance (EPR) measurements of natural anhydrite CaSO₄, celestite SrSO₄ and barite BaSO₄ have revealed the presence of PO ₃ ^2? and SO ₃ ^? radicals. Hyperfine structure from³³S has been detected and measured for the first time. Low-symmetry effects, which are manifested in noncoincidence of g and hyperfine axes, were observed for SO ₃ ^? . The dynamics of one of the two SO ₃ ^? types in anhydrite has been investigated. Variations of spin Hamiltonian parameters with temperature have been attributed to thermally induced jumps between the two magnetically inequivalent sites of this center.     

Assessment of hydrogeochemical processes in a coastal region: Application of multivariate statistical model

Hydrogeochemical studies have been carried out in a coastal region, using multivariate statistical model, for better understanding the controlling processes that influence the aquifer chemistry. Two principal components (PC1 and PC2) are extracted from the data set of chemical variables (pH, TDS, Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO ₃ ^? , Cl^?, SO ₄ ^2? , NO ₃ ^? and F^?), which account for 79% of the total variation in the quality of groundwater. The PC1 (salinity controlled process) includes the concentrations of TDS, Mg²⁺, Na⁺, K⁺, Cl^?, SO ₄ ^2? and NO ₃ ^? , while the PC2 (alkalinity controlled process) comprises the concentrations of pH, HCO ₃ ^? and F^?. The spatial distribution of PC scores identifies the locations of high salinity and alkalinity processes. The first process corresponds to the influences of geogenic, anthropogenic and marine sources, and the second one to the influence of water-soil-rock interaction. Thus, the present study shows the usefulness of multivariate statistical model as an effective means of interpretation of spatial controlling processes of groundwater chemistry.     

The electronic structure and absorption spectrum of MnO 6 9− octahedra in manganian andalusite

The energy levels of MnO ₆ ^9? clusters, with D _4h approximated and C _2v actual symmetry of the M ₁ site of Mn³⁺-bearing andalusite, are calculated using the multiple scattering method. The energies of the electronic d-d transition of Mn³⁺ in the clusters with D _4h symmetry are calculated to be 6,000–7,000 cm^?1 (⁵ B _1g → ⁵ A _1g ), ～18,000 cm^?1 (⁵ B _1g → ⁵ B _2g ) and ～19,000 cm^?1 (⁵ B _1g → ⁵ E _g ). Apart from a splitting of the ⁵ E _g -level into two levels separated by 300–350 cm^?1, no significant changes of these transition energies are noted for the corresponding cluster with C _2v symmetry. The calculated transition energies give a good fit to the structure of the optical absorption spectra of Mn³⁺-bearing andalusites and support recent assignments of the major absorption bands observed in these spectra.     

Luminescence centers in anhydrite,barite, celestite and their synthesized analogs

The intrinsic luminescence center (LC) of SO ₄ ^2? appears at 360 nm in all types of sulfates, but is absent in sulfates with large quantities of impurities. Three nonequivalent Gd³⁺ LC have been observed in luminescence spectra of anhydrite. Gd³⁺, Ce³⁺ O ₂ ^? LC were established in celestite. Photoluminescence (PL) bands in the sulfates were assigned as follows: the band at 460 nm is related to Eu²⁺ (a connection with Al³⁺ or donor-acceptor pair is possible also) in sulfates of Ca and Ba; bands at 520 nm and 590 nm are related to VO₄, MoO₄ and TiO₄ substituting SO₄; the band at 660 nm is assigned to Ti³⁺ X-ray luminescence (XL) band at 620 nm is assigned to Ag⁺.     

Thermodynamics of plagioclase II: Temperature evolution of the spontaneous strain at the I\bar 1 \leftrightarrow P\bar 1 phase transition in anorthite

The temperature dependence of the lattice parameters of pure anorthite with high Al/Si order reveals the predicted tricritical behaviour of the \(I\bar 1 \leftrightarrow P\bar 1\) phase transition at T _c ^* =510 K. The spontaneous strain couples to the order parameter Q° as x _i∝S _xQ ⁱ Q°² with S _xQ ¹ =4.166×10^?3, S _xQ ² =0.771×10^?3, S _xQ ³ =?7.223×10^?3 for the diagonal elements. The temperature dependence of Q° is $$Q^{\text{o}} = \left( {1 - \frac{T}{{510}}} \right)^\beta ,{\text{ }}\beta = \tfrac{{\text{1}}}{{\text{4}}}$$ A strong dependence of T _c ^* , S _xQ ⁱ and β is predicted for Al/Si disordered anorthite.     

Thermodynamics of plagioclase III: Spontaneous strain at the I\overline 1 - P\overline 1 phase transition in Ca-rich plagioclase

The lattice parameters of anorthites An₉₈Ab₂ and An₁₀₀ have been measured from 22 to 1100 K. The spontaneous strain arising from the \(I\overline 1 - P\overline 1\) displacive transition in An₉₈ follows second order Landau behaviour. The spontaneous strain (? _s) couples quadratically to the order parameter (Q ⁰) with ? _s∝Q ⁰²∝(T _c ^* ?T) and T _c ^* =530 K in An₉₈. This is in contrast to the tricritical behaviour observed in pure anorthite. These observations are consistent with a Landau model for the free energy of Ca-rich plagioclases in which Al/Si order and Na content renormalize the fourth order coefficient.     

Electronic and magnetic structure of pyroxenes: II. Orthoferrosilite

The electronic and magnetic structure of the chain silicate orthoferrosilite Fe ₂ ²⁺ Si₂O₆ has been investigated by electronic structure calculations in the local spin density approximation. All calculations are based on experimentally determined geometrical data at room temperature. The calculated spin-allowed d–d excitation energies and hyperfine parameters are in quantitative agreement with the respective experimental data from optical absorption and Mössbauer spectroscopy. Inside one ribbon that is parallel to the crystallographic c axis and contains two non-equivalent M1 and M2 sites, all iron spins are ferromagnetically coupled with coupling constants of about +16 cm^?1. Between these ribbons within the (b, c)-plane a weak ferromagnetic coupling of about +2 cm^?1 is obtained. Neighboured (b, c)-planes are coupled antiferromagnetically via chains of Si ^B -tetrahedra but ferromagnetically via chains of Si ^A -tetrahedra. Such a theoretically determined "double-plane antiferromagnetic" spin structure is at variance with an experimentally derived magnetic structure. This discrepancy is attributed to differences between the geometry at room temperature and at temperatures below the Néel temperature currently not available.     

First principles quantum mechanical calculation of the electric dipole polarizabilities of the borate,carbonate, nitrate and related ions

Electric dipole polarizabilities have been calculated from first principles of quantum mechanics for the BO ₃ ^3? , CO ₃ ^2? , NO ₃ ^? series and for NO ₂ ^? and LiNO₃(g). Calculated trends in average polarizability and polarizability anisotropy in the BO ₃ ^3? -NO ₃ ^? series are in agreement with experiment and can be qualitatively interpreted in terms of the varying energies of the a₁′, a₂″ and e′ symmetry unoccupied MO's of the oxyanions. Embedding a CO ₃ ^2? ion in a D_3h symmetry array of divalent cations reduces both the average polarizability and its anisotropy, particularly when diffuse s and p functions are included in the calculation. Calculations on the gas phase LiNO₃ molecule and on the free NO ₃ ^? ion in the distorted geometry found in LiNO₃(g) allow us to separate polarizability contributions internal to the NO ₃ ^? and Li⁺ ions from those which arise from the Li⁺-NO ₃ ^? interaction. The Li⁺-NO ₃ ^? interaction term so obtained is much smaller than the NO ₃ ^? contribution but is in turn larger than the Li⁺ contribution, suggesting that the inclusion of this interaction term is essential for obtaining accurate results for ion pairs. Although static polarizabilities are in reasonable agreement with experiment for NO ₃ ^? the wavelength dispersion of the polarizability is underestimated by about a factor of two, apparently as a result of inadequacies in the quantum mechanical method. Calculated values are also presented for ¹⁴N NMR shieldings in the nitrogen oxyanions but these are in only qualitative agreement with the experimental values. Similarly, calculated values of magnetic susceptibility are in only qualitative agreement with experiment although trends along the BO ₃ ^3? -NO ₃ ^? series are properly reproduced.     

Equation of state of Fe3+-bearing phase-X

We investigated the high-pressure behaviour of Fe³⁺-bearing hydrous phase-X, (K_1.307Na_0.015)(Mg_1.504Fe _0.373 ³⁺ Al_0.053Ti _0.004 ⁴⁺ )Si₂O₇H_0.36, up to 34?GPa at room temperature by synchrotron X-ray powder diffraction. The lattice parameters behave anisotropically, with the [001] direction stiffer than [100]. In the 10^?4 to 22?GPa pressure range, the axial bulk moduli are K _0a ?=?112(3) GPa and K′?=?4, and K _0c ?=?158(2) GPa and K′?=?4, and the anisotropy of the lattice parameters is β_0c :β_0a ?=?0.71:1. The cell volumes are fitted by a second-order Birch–Murnaghan equation of state giving a bulk modulus of K ₀?=?127(1) GPa and K′?=?4 in the same pressure range. After 22?GPa, a discontinuity in volume and lattice parameters can be recognized. Sample did not become amorphous up to 34?GPa. The coupled substitution K?+?Mg?=?[]?+?Fe³⁺ has only a limited influence on the bulk modulus and structural stability of phase-X.     

Laihunite—A new iron silicate mineral

Laihuite reported in the present paper is a new iron silicate mineral found in China with the following characteristics:

1. This mineral occurs in a metamorphic iron deposit, associated with fayalite, hypersthene, quartz, magnetitc, etc.
2. The mineral is opaque, black in colour, thickly tabular in shape with luster metallic to sub-metallic, two perfect cleavages and specific gravity of 3.92.
3. Its main chemical components are Fe and Si with Fe³⁺>Fe²⁺. The analysis gave the formula of Fe Fe _1.00 ³⁺ ·Fe _0.58 ²⁺ ·Mg _0.03 ²⁺ ·Si_0.96O₄.
4. Its DTA curve shows an exothermic peak at 713°C.
5. The mineral has its own infrared spectrum distinctive from that of other minerals.
6. This mineral is of orthorhombic system; space group:C _2h ^/5 ?P2₁/c; unit cell:α=5.813ű0.005,b=4.812ű0.005,c=10.211ű0.005,β=90.87°.
7. The Mössbauer spectrum of this mineral is given, too.

     

EPR study of chromium-doped forsterite crystals: Cr3+(M1) with associated trivalent ions Al3+ and Sc3+

Electron paramagnetic resonance (EPR) study of single crystals of forsterite co-doped with chromium and scandium has revealed, apart from the known paramagnetic centers Cr³⁺(M1) and Cr³⁺(M1)– $ V_{{{\text{Mg}}^{2 + } }} $ (M2) (Ryabov in Phys Chem Miner 38:177–184, 2011), a new center Cr³⁺(M1)– $ V_{{{\text{Mg}}^{2 + } }} $ (M2)–Sc³⁺ formed by a Cr³⁺ ion substituting for Mg²⁺ at the M1 structural position with a nearest-neighbor Mg²⁺ vacancy at the M2 position and a Sc³⁺ ion presumably at the nearest-neighbor M1 position. For this center, the conventional zero-field splitting parameters D and E and the principal g values have been determined as follows: D?=?33,172(29) MHz, E?=?8,482(13) MHz, g?=?[1.9808(2), 1.9778(2), 1.9739(2)]. The center has been compared with the known ion pair Cr³⁺(M1)–Al³⁺ (Bershov et al. in Phys Chem Miner 9:95–101, 1983), for which the refined EPR data have been obtained. Based on these data, the known sharp M1″ line at 13,967?cm^?1 (with the splitting of 1.8?cm^?1), observed in low-temperature luminescence spectra of chromium-doped forsterite crystals (Glynn et al. in J Lumin 48, 49:541–544, 1991), has been ascribed to the Cr³⁺(M1)–Al³⁺ center. It has been found that the concentration of the new center increases from 0 up to 4.4?×?10¹⁵?mg^?1, whereas that of the Cr³⁺(M1) and Cr³⁺(M1)– $ V_{{{\text{Mg}}^{2 + } }} $ (M2) centers quickly decreases from 7.4?×?10¹⁵?mg^?1 down to 3?×?10¹⁵?mg^?1 and from 2.7?×?10¹⁵?mg^?1 down to 0.5?×?10¹⁵?mg^?1, i.e., by a factor of 2.5 and 5.4, respectively, with an increase of the Sc content from 0 up to 0.22 wt?% (at the same Cr content 0.25 wt?%) in the melt. When the Sc content exceeds that of Cr, the concentration of the new center decreases most likely due to the formation of the Sc³⁺(M1)– $ V_{{{\text{Mg}}^{2 + } }} $ (M2)–Sc³⁺ complex instead of the Cr³⁺(M1)– $ V_{{{\text{Mg}}^{2 + } }} $ (M2)–Sc³⁺ center. The formation of such ordered neutral complex is in agreement with the experimental results, concerning the incorporation of Sc into olivine, recently obtained by Grant and Wood (Geochim Cosmochim Acta 74:2412–2428, 2010).     

The effect of medium chemistry on the solubility and morphology of brushite crystals

An experimental study of the particulars of the solubility and crystallization of brushite Ca(HPO₄) · 2H₂O from aqueous solution in conditions of a variable pH (6.0–3.0) and the contents of impurity ions (K⁺, Na⁺, NH ₄ ⁺ , Mg²⁺, SO ₄ ^2? , CO ₃ ^2? ) has been conducted. It is established that brushite solubility markedly rises with a decrease in pH from 6 to 3 and slightly rises with an increase in Mg²⁺ and SO ₄ ^2? concentrations. The enrichment in K⁺, Na⁺, and NH ₄ ⁺ does not affect brushite solubility. The changeable chemistry of the medium results in variation of the synthetic crystal habit, from rhombic tabular to thickened prismatic crystals.     

Electronic absorption spectra of chromium-bearing sapphirine

Violet, non-pleochroic and greenish-blue, pleochroic chromium-substituted sapphirines were found in corundum-bearing spinel-websterite xenolites from the Yakutian kimberlite pipes Noyabrskaya (N) and Sludyanka (Sl), respectively. The crystallochemical formulae of sapphirine crystals from such xenolites were determined by EMP to be (Mg_3.40Fe_0.23Al_3.25Cr_0.16)^[6] Al _1.00 ^[6] [O₂/Al_4.53Si_1.47O₁₈] (N) and (Mg_2.53Fe_0.55 Mn_0.04Ti _0.03 ⁴⁺ Al_3.55Cr _0.08 ³⁺ )^[6]Al _1.00 ^[16] [O₂/Al_4.28Si_1.73O₁₈] (Sl). Single crystal spectra in the range 35000–6000 cm^1- showed a slightly polarization dependent absorption edge near 3200 cm^1- (N) or 30000 cm^1- (Sl) and unpolarized bands at 25300 and 17300 cm^1-, typical of spin-allowed transitions, derived from ⁴A_2g→⁴T_1g and ⁴A_2g→⁴T_2g, of Cr³⁺ in octahedral sites, with point symmetry C₁, of the structure. Another weak band at 23000 cm^?1 in the sapphirine-N spectra is attributed to low symmetry splitting of the excited ⁴T₁ (F)-State of Cr³⁺. These assignments lead to crystal field parameters Dq=1730cm^?1 and B= 685cm^?1 of Cr³⁺ in sapphirine. Crystallochemical and spectroscopic arguments suggest that Cr³⁺ subsitutes for Al in the M(1) or M(8) sites of the sapphirine structure. In addition to Cr³⁺-transitions, spectra of Sl exhibit weak dd-bands of Fe²⁺ at 10000 and 7700 cm^1-, which are unpolarized in consistency with the C₁ site symmetry of the octahedra in the structure. Spectra of Sl show also prominent, broad bands (Δv_1/2～-5000 cm^1-) at 15000 and 11000 cm^1-, which occur in E//Y(//b) and E//Z(//_c=12°) only and exhibit an intensity ratio α_Y∶α_z close to 1∶3. This result, the large half width, as well as band energy — MM distance considerations suggest that these bands originate from Fe^2+[6]-Fe^3+[6] charge-transfer transitions in wall octahedra M(1)M(2), M(6)M(7) etc., forming MM vectors of 30° with the c-axis. The lack of Fe²⁺-Fe³⁺ charge-transfer bands in sapphirine N might indicate a lower oxygen fugacity during the formation of the websterite from the Noyabrskaya pipe compared to that from the Sludyanka pipe.