Experimental study on the phase equilibria in the join CaMgSi2O6-CaCrCrSiO6 with special reference to the blue diopside

The behaviour of tetrahedrally coordinated and octahedrally coordinated Cr³⁺ ions in diopside is discussed from the study on the join CaMg-Si₂O₆-CaCrCrSiO₆. The molecule CaCrCrSiO₆ decomposes into uvarovite+eskolaite and its maximum solubility in diopside is 6.7 wt percent at 940 ° C. Crystalline phases are diopside ss (ss is abbreviation of solid solution), uvarovite ss, wollastonite ss, spinel and eskolaite. The diopside ss is blue in colour. Its optical spectra were measured in the wavelenght range of 325–2600 nm, and assigned after tetrahedral configuration Td and octahedral configuration Oh. It is estimated that octahedral Cr³⁺ ions are in high spin state, while tetrahedral Cr³⁺ ions may be probably in low spin state. The _t and B are 10,300–10,370 cm^–1 and 429–432 cm^–1. The CFSE for tetrahedral low spin Cr³⁺ ions is nearly the same as that for octahedral high spin Cr³⁺ ions. The ionic radii of tetrahedral low spin Cr³⁺ ions calculated are 0.47–0.53 Å, shrinked from the radius of octahedral high spin Cr³⁺ ion (0.615 Å) as much as 14–24 percent. Petrologic implications of the result are also discussed.The first half of the D. Sc. dissertation of K. Ikeda presented to Hokkaido University in June, 1976     

Spectroscopic characterisation and crystal field calculations of varicoloured kyanites from Loliondo, Tanzania

Orange, ochre-coloured, light green and dark blue varieties of kyanite, ideally Al₂SiO₅, from Loliondo, Tanzania, have been characterised by electron microprobe analysis and polarised infrared and optical absorption spectroscopy. All colour varieties show elevated Fe contents of 0.39 to 1.31 wt.% FeO, but Ti contents only in the range of the EMP detection limit. Orange and ochre-coloured crystals have Mn contents of 0.23 and 0.06 wt.% MnO, respectively, the dark blue kyanite contains 0.28 wt.% Cr₂O₃, while the light green sample is nearly free from transition metal cations other than Fe. Polarised infrared spectra reveal OH defect concentrations of 3 to 17 wt.ppm H₂O with structural OH defects partially replacing the O_B (O2) oxygen atoms. Polarised optical absorption spectra show that the colour of all four varieties is governed by crystal field d-d transitions of trivalent cations, i.e. Fe³⁺ (all samples), Mn³⁺ (orange and ochre) and Cr³⁺ (blue kyanite), replacing Al in sixfold coordinated triclinic sites of the kyanite structure. Intervalence charge transfer, the prevalent colour-inducing mechanism in ‘usual’ (Cr-poor) blue kyanites, seems to play a very minor, if any, role in the present samples. Crystal field calculations in both a ‘classic’ tetragonal and in the semiempirical Superposition Model approach, accompanied by distance- and angle-least-squares refinements, indicate that Fe³⁺ preferably occupies the Al4 site, Cr³⁺ prefers the Al1 and Al2 sites, and Mn³⁺ predominantly enters the Al1 site. In each case specific local relaxation effects were observed according to the crystal chemical preferences of these transition metal cations. Furthermore, the high values obtained in the calculations for the interelectronic repulsion parameter Racah B correspond to a high ionic contribution to Me³⁺–O bonding in the kyanite structure. In the particular case of the blue sample, band positions specifically related to the high Racah B value enable this ‘unusual’ type of blue colouration of kyanite solely due to Cr³⁺ cations.     

Luminescence and other spectroscopic properties of purple and green Cr-clinochlore

For the first time ever, the luminescence spectra of Cr³⁺ centers in two chlorite crystals are presented. Chromium ions occupy the strong crystal-field site M4 in the brucite sheet and the intermediate crystal-field site in the inner octahedral sheet for purple and green chlorite, respectively. We discuss the influence of an effective positive charge on the Cr³⁺ ion and an effective negative charge of ligands on the differences in the values of the Dq and B parameters. It is concluded that the presence of Fe²⁺ ions and other point defects, as well as concentration quenching, causes the very short luminescence lifetimes of chromium ions.     

绿柱石中铁离子的晶格占位及致色作用

绿柱石族宝石颜色丰富,一直是市场上重要的宝石品种。几十年来,国内外学者对不同颜色绿柱石的致色机理及改色工艺开展了广泛的研究。铁离子作为重要的致色过渡金属离子之一,其价态调控是绿柱石改色工艺的关键,所以铁离子的价态、晶格占位和对应的致色作用也一直是绿柱石研究的焦点。铁离子被认为可能存在于绿柱石中的铝氧八面体Al³⁺格位、硅氧四面体Si⁴⁺格位、铍氧四面体Be²⁺格位、结构通道2a或2b位和晶格间隙6g位等位置,是蓝、绿或黄等颜色绿柱石的主要致色元素。本文通过对绿柱石的晶体结构、铁离子的核外电子排布和晶格占位等方面文献资料的梳理及综合分析,认为Fe²⁺和Fe³⁺分别对蓝色和黄色绿柱石的呈色起着主导作用。当Fe²⁺和Fe³⁺处于晶格中不同位置时致色作用的具体差异,仍有待于进一步研究。     

Distinct ruby suite at Sardapur, Orissa: A spectroscopic investigation

Orissa is an important area for gem variety of corundum deposits in India. Spectroscopic studies, such as ESR, OAS on samples from Sardapur, Orissa, were carried out to ascertain the colour cause of corundum. Electron spin resonance (ESR) spectroscopic study was carried out on the samples to detect the presence of paramagnetic ions i.e. Fe²⁺, Fe³⁺, Ti⁴⁺, Cr³⁺ and V³⁺ etc. The variable temperature experiment carried out to observe the effect of heating on peak valence state change in paramagnetic ions. Samples were cut and polished to obtain the optical absorption spectrum (OAS) to detect the colour causing transition ions/defect centres. The samples of gem variety were step heated up to 300°C for colour enhancement studies. EPMA analysis has revealed the low chromium concentration in the rubies. The varying hues of red in the corundum are due to the presence of bivalent and trivalent iron and charge transfer process along with Cr³⁺ absorption in the 550 nm region.     

Prediction of Gibbs free energies of formation of minerals of the alunite supergroup

A method for the prediction of Gibbs free energies of formation for minerals belonging to the alunite family is proposed, based on an empirical parameter Δ_GO⁼ M^z+(c) characterizing the oxygen affinity of the cation M^z+. The Gibbs free energy of formation from constituent oxides is considered as the sum of the products of the molar fraction of an oxygen atom bound to any two cations, multiplied by the difference of oxygen affinity Δ_GO⁼ M^z+(c) between any two consecutive cations. The Δ_GO⁼ M^z+(c) value, using a weighing scheme involving the electronegativity of a cation in a specific site (12-fold coordination site, octahedral and tetrahedral) is assumed to be constant. It can be calculated by minimizing the difference between experimental Gibbs free energies (determined from solubility measurements) and calculated Gibbs free energies of formation from constituent oxides. Results indicate that this prediction method gives values within 0.5% of the experimentally measured values. The relationships between Δ_GO⁼ M^z+(alunite) corresponding to the electronegativity of a cation in either dodecahedral sites, octahedral sites or tetrahedral sites and known as Δ_GO⁼ M^z+(aq) were determined, thereby allowing the prediction of the electronegativity of rare earth metal ions and trivalent ions in dodecahedral sites and highly charged ions in tetrahedral sites. This allows the prediction of Gibbs free energies of formation of any minerals of the alunite supergroup (bearing various ions located in the dodecahedral and tetrahedral sites). Examples are given for hydronium jarosite and hindsalite, and the results appear excellent when compared to experimental values.     

Chromium and vanadium impurities in natural green euclase and their relation to the color

Natural specimens of green gemological euclase (chemical formula BeAlSiO₄(OH)) from Brazil were investigated by electron paramagnetic resonance (EPR) and optical absorption. In addition to iron-related EPR spectra, analyzed recently in blue and colorless euclase, chromium and vanadium-related EPR spectra were also detected in green euclase. Their role as color causing centers is discussed. The results indicate that Cr³⁺ ions substitute for Al³⁺ ions in the euclase structure. The EPR rotation patterns of Cr³⁺ with electron spin S = 3/2 were analyzed with monoclinic spin Hamiltonian leading to the parameters of g _xx , g _yy and g _zz equal to 2.018, 2.001 and 1.956 and electronic fine structure parameters of D = −8.27 GHz and E = 1.11 GHz, respectively, with high asymmetry ratio E/D = 0.13. For the vanadium-related EPR spectra the situation is different. It is concluded that vanadium is incorporated as the vanadyl radical VO²⁺ with electron spin S = 1/2 with nearly axial spin Hamiltonian parameters g_zz = 1.9447, g _xx  = 1.9740 g _yy  = 1.9669 and axial hyperfine interactions due to the nuclear spin I = 7/2 of the ⁵¹V isotope leading to A _zz  = 502 MHz, A _xx  = 150 MHz and A _yy  = 163 MHz. The green color of euclase is caused by two strong broad absorption bands centered at 17,185 and 24,345 cm⁻¹ which are attributed to the ⁴A_2g → ⁴T_2g, ⁴T_1g transitions of Cr³⁺, respectively. Vanadyl radicals may introduce some absorption bands centered in the near infrared with tail extending into the visible spectral range.     

Incorporation of Cr<Superscript>3+</Superscript> in dickite: a spectroscopic study

 We have investigated a well-ordered sample of natural Cr-bearing dickite from Nowa Ruda (Lower Silesia, Poland) using electron paramagnetic resonance (EPR) at X- and Q-band frequencies (9.42 and 33.97 GHz, respectively) and optical diffuse reflectance spectroscopy. The observation of the spin-forbidden transitions at 15500 and 14690 cm⁻¹ allows us to unambiguously identify the major contribution of octahedrally coordinated Cr³⁺ ions in the optical spectrum. The X- and Q-band EPR spectra show two superposed Cr³⁺ signals. The corresponding fine-structure parameters were determined at room temperature and 145 K. These results suggest the substitution of Cr³⁺ for Al³⁺ in equal proportions in the two unequivalent octahedral sites of the dickite structure. In kaolin group minerals, the distortion around Cr³⁺ ions (λ≈ 0.2–0.4) in Al sites is significantly less rhombic than that observed around Fe³⁺ ions (λ≈ 0.6–0.8). Received: 29 June 2001 / Accepted: 22 October 2001     

Structural changes and valence states in the MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript>–FeCr<Subscript>2</Subscript>O<Subscript>4</Subscript> solid solution series

The influence on the structure of Fe²⁺ Mg substitution was studied in synthetic single crystals belonging to the MgCr₂O₄–FeCr₂O₄ series produced by flux growth at 900–1200 °C in controlled atmosphere. Samples were analyzed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption-, infrared- and Mössbauer spectroscopy. The Mössbauer data show that iron occurs almost exclusively as ^IVFe²⁺. Only minor Fe³⁺ (<0.005 apfu) was observed in samples with very low total Fe. Optical absorption spectra show that chromium with few exceptions is present as a trivalent cation at the octahedral site. Additional absorption bands attributable to Cr²⁺ and Cr³⁺ at the tetrahedral site are evident in spectra of end-member magnesiochromite and solid-solution crystals with low ferrous contents. Structural parameters a₀, u and T–O increase with chromite content, while the M–O bond distance remains nearly constant, with an average value equal to 1.995(1) Å corresponding to the Cr³⁺ octahedral bond distance. The ideal trend between cell parameter, T–O bond length and Fe²⁺ content (apfu) is described by the following linear relations: a₀=8.3325(5) + 0.0443(8)Fe²⁺ (Å) and T–O=1.9645(6) + 0.033(1)Fe²⁺ (Å) Consequently, Fe²⁺ and Mg tetrahedral bond lengths are equal to 1.998(1) Å and 1.965(1) Å, respectively.     

Cation distribution and structure modelling of spinel solid solutions

 This paper presents an improved generalisation of cation distribution determination based on an accurate fit of all crystal-chemical parameters. Cations are assigned to the tetrahedral and octahedral sites of the structure according to their scattering power and a set of bond distances optimised for spinel structure. A database of 295 spinels was prepared from the literature and unpublished data. Selected compositions include the following cations: Mg²⁺, Al³⁺, Si⁴⁺, Ti⁴⁺, V³⁺, Cr³⁺, Mn²⁺, Mn³⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺, Zn²⁺ and vacancies. Bond distance optimisation reveals a definite lengthening in tetrahedral distance when large amounts of Fe³⁺ or Ni²⁺ are present in the octahedral site. This means that these cations modify the octahedral angle and hence the shared octahedral edge, causing an increase in the tetrahedral distance with respect to the size of the cations entering it. Some applications to published data are discussed, showing the capacity and limitations of the method for calculating cation distribution, and for identifying inconsistencies and inaccuracies in experimental data. Received: 19 February 2001 / Accepted: 1 June 2001     

Synthetic and natural chromium-bearing spinels: an optical spectroscopy study

Four samples of synthetic chromium-bearing spinels of (Mg, Fe²⁺)(Cr, Fe³⁺)₂O₄ composition and four samples of natural spinels of predominantly (Mg, Fe²⁺)(Al, Cr)₂O₄ composition were studied at ambient conditions by means of optical absorption spectroscopy. Synthetic end-member MgCr₂O₄ spinel was also studied at pressures up to ca. 10 GPa. In both synthetic and natural samples, chromium is present predominantly as octahedral Cr³⁺ seen in the spectra as two broad intense absorption bands in the visible range caused by the electronic spin-allowed ⁴ A _2g  → ⁴ T _2g and ⁴ A _2g  → ⁴ T _1g transitions (U- and Y-band, respectively). A distinct doublet structure of the Y-band in both synthetic and natural spinels is related to trigonal distortion of the octahedral site in the spinel structure. A small, if any, splitting of the U-band can only be resolved at curve-fitting analysis. In all synthetic high-chromium spinels, a couple of relatively narrow and weak bands of the spin-allowed transitions ⁴ A _2g  → ² E _g and ⁴ A _2g  → ² T _1g of Cr³⁺, intensified by exchange-coupled interaction between Cr³⁺ and Fe³⁺ at neighboring octahedral sites of the structure, appear at ~14,400 and ~15,100 cm^?1. A vague broad band in the range from ca. 15,000 to 12,000 cm^?1 in synthetic spinels is tentatively attributed to ^IVCr²⁺ + ^VICr³⁺ → ^IVCr³⁺ + ^VICr²⁺ intervalence charge-transfer transition. Iron, mainly as octahedral Fe³⁺, causes intense high-energy absorption edge in near UV-range (ligand–metal charge-transfer O^2? → Fe³⁺, Fe²⁺ transitions). As tetrahedral Fe²⁺, it appears as a strong infrared absorption band at around 4,850 cm^?1 caused by electronic spin-allowed ⁵ E → ⁵ T ₂ transitions of ^IVFe²⁺. From the composition shift of the U-band in natural and synthetic MgCr₂O₄ spinels, the coefficient of local structural relaxation around Cr³⁺ in spinel MgAl₂O₄–MgCr₂O₄ system was evaluated as ~0.56(4), one of the lowest among (Al, Cr)O₆ polyhedra known so far. The octahedral modulus of Cr³⁺ in MgCr₂O₄, derived from pressure-induced shift of the U-band of Cr³⁺, is ~313 (50) GPa, which is nearly the same as in natural low-chromium Mg, Al-spinel reported by Langer et al. (1997). Calculated from the results of the curve-fitting analysis, the Racah parameter B of Cr³⁺ in natural and synthetic MgCr₂O₄ spinels indicates that Cr–O-bonding in octahedral sites of MgCr₂O₄ has more covalent character than in the diluted natural samples. Within the uncertainty of determination in synthetic MgAl₂O₄ spinel, B does not much depend on pressure.     

The effect of thermal treatment on the 57Fe Mössbauer spectrum of beryl

Mössbauer spectra (MS) of blue, green and yellow beryl (ideally Be₃Al₂Si₆O₁₈) containing approximately 1% of iron were obtained at 295 and 500 K. Room temperature (RT) spectra of both blue and green samples showed the presence of an asymmetric Fe²⁺ doublet (ΔE _Q~2.7 mm/s, δ~1.1 mm/s), with a very broad low-velocity peak. There is no clear evidence for the presence of a ferric component. The MS of the yellow sample at RT consists of an intense central absorption with parameters typical for Fe³⁺ (ΔE _Q~0.4 mm/s, δ~0.29 mm/s), plus an apparently symmetrical Fe²⁺ doublet. This sample acquires a light-blue shade upon heating in air at about 620 K. Thermal treatments at high temperatures caused no significant changes in the MS, but the green and yellow beryl acquire a blue colour. All these results are interpreted in relation to the existence of channel water and the distribution of iron among the available crystallographic sites.     

On the occurrence and stability of divalent chromium in olivines included in diamonds

Olivine inclusions in diamonds from kimberlites originating from the deep Upper Mantle contain significant amounts of chromium. It has been suggested that divalent chromium occurs in these olivines. This hypothesis is supported by recent Mössbauer and electronic spectral measurements at high pressures, which demonstrate that pressure-induced reduction takes place in compounds and minerals initially containing Fe³⁺, Mn³⁺, and Cu²⁺ ions. The process is facilitated at high temperatures. Low oxidation states of other metals such as Cr(II) are expected to be stabilized under the very high pressures and elevated temperature conditions in the Mantle. Since Cr²⁺ ions are susceptible to the Jahn-Teller effect, they are predicted by crystal field theory to be stabilized in certain distorted coordination sites, such as the olivine Ml site, all three sites of the -spinel phase, and the 7-coordinated site of the strontium plumbate structure-type. The Cr²⁺ ions in olivines are stabilized in kimberlites intruded into the Crust by the high confining pressures in the diamond inclusions.     

Electron spin resonance of trivalent chromium in forsterite,Mg2SiO4

The electron spin resonance (ESR) spectrum of Cr³⁺ in a synthetic single crystal of forsterite doped with Cr₂O₃ was studied at room temperature in the X-band frequency range. The dependence of the observed spectra on the crystal orientation with respect to the applied magnetic field was investigated. The ESR spectra are described by the spin Hamiltonian \(H = \beta HgS + D(S_Z^{\text{2}} - {\text{1/3}}S{\text{(}}S{\text{ + 1)) + }}E{\text{(}}S_x^{\text{2}} - S_y^{\text{2}} {\text{)}}\) with S=3/2. The spin resonance reveals that the chromium ions are located at both the M1 and M2 positions. Other possible substitutional or interstitial Cr³⁺ positions may be possible, but were not observed. The site occupancy numbers of Cr³⁺ at M1 and M2 are roughly 1.2×10^?4 and 0.8×10^?4, respectively, assuming that chromium is oxidized completely. The preference of the chromium ions for M1 was interpreted qualitatively in terms of crystal field criteria. The rhombic and axial spin Hamiltonian parameters, D and E, and the directions of the magnetic axes obtained for M1 and M2 are consistent with the respective oxygen coordination polyhedra.     

Correlation of spectroscopic properties and substitutional sites of Cr3+ in aluminosilicates: II. Andalusite and sillimanite

This paper is an extension of the earlier one dealing with kyanite in which the best fitting value of the oxygen ligand distance for Cr³⁺ is adopted to study the spectroscopic properties of Cr³⁺ ions doped at the two possible Al sites in the other two polymorphs of the aluminosilicate group (Al₂O₃ · SiO₂), namely, andalusite and sillimanite. The superposition model and the crystal field analysis package recently developed for 3d ions doped at arbitrary low symmetry sites in crystals are used to predict energy levels and statevectors within the whole 3d ³ configuration. Then the values of the ground state zerofield splitting for Cr³⁺ ions at each Al sites in the two crystals are obtained. The splittings of the lower excited states ² E and ⁴ T ₂ as well as the admixture of ⁴ T ₂ into ² E have also been predicted. Comparison of our results with the available experimental data enable us to correlate the optical and EPR Spectroscopic properties with the substitutional Cr³⁺ sites. The conclusion is that in andalusite and sillimanite only the Al sites with nearly-octahedral six-fold coordination seem to be occupied by Cr³⁺ ions.     

The effect of valence state and site geometry on Cr L3,2 electron energy-loss spectra of Cr-bearing oxidic compounds

Chromium L_3,2 energy loss near-edge structures (ELNES) of nine chromium compounds were measured in a transmission electron microscope to study the effect of valence state and site geometry of chromium on spectral features. The compounds studied represent a set of standards with given valence state and coordination. The chromium coordination is either octahedral or tetrahedral with different degree of distortion. The distortion of polyhedra results in a loss of the fine detail of spectral features in Cr L_3,2 ELNES spectra. The effect of valence state manifests in a systematic chemical shift of the ELNES spectra by about 2 eV per oxidation state for octahedrally coordinated Cr and 0.4–1.4 eV per oxidation state for tetrahedrally coordinated Cr. On the basis of collected Cr L_3,2 ELNES spectra we propose a simple quantification technique for the determination of chromium oxidation state in oxidic compounds which is independent of the coordination.     

Chromium solubility in MgSiO3 ilmenite at high pressure

The crystal structure and chemical composition of crystals of (Mg_1?x Cr _x )(Si_1?x Cr _x )O₃ ilmenite (with x = 0.015, 0.023 and 0.038) synthesized in the model system Mg₃Cr₂Si₃O₁₂–Mg₄Si₄O₁₂ at 18–19 GPa and 1,600 °C have been investigated. Chromium was found as substitute for both Mg at the octahedral X site and Si at the octahedral Y site, according to the reaction Mg²⁺ + Si⁴⁺ = 2Cr³⁺. Such substitutions cause a shortening of the <X–O> and a lengthening of the <Y–O> distances with respect to the values typically observed for pure MgSiO₃ ilmenite and eskolaite Cr₂O₃. Although no high Cr contents are considered in the pyrolite model, Cr-bearing ilmenite may be the host for chromium in the Earth’s transition zone. The successful synthesis of ilmenite with high Cr contents and its structural characterization are of key importance because the study of its thermodynamic constants combined with the data on phase relations in the lower-mantle systems can help in the understanding of the seismic velocity and density profiles of the transition zone and the constraining composition and mineralogy of pyrolite in this area of the Earth.     

Raman study of MgCr2O4–Fe2+Cr2O4 and MgCr2O4–MgFe2 3+O4 synthetic series: the effects of Fe2+ and Fe3+ on Raman shifts

Two synthetic series of spinels, MgCr₂O₄–Fe²⁺Cr₂O₄ and MgCr₂O₄–MgFe₂ ³⁺O₄ have been studied by Raman spectroscopy to investigate the effects of Fe²⁺ and Fe³⁺ on their structure. In the first case, where Fe²⁺ substitutes Mg within the tetrahedral site, there is a continuous and monotonic shift of the Raman modes A_1g and E_g toward lower wavenumbers with the increase of the chromite component into the spinel, while the F_2g modes remain nearly in the same position. In the second series, for low Mg-ferrite content, Fe³⁺ substitutes for Cr in the octahedral site; when the Mg-ferrite content nears 40 %, a drastic change in the Raman spectra occurs as Fe³⁺ starts entering the tetrahedral site as well, consequently pushing Mg to occupy the octahedral one. The Raman spectral region between 620 and 700 cm^?1 is associated to the octahedral site, where three peaks are present and it is possible to observe the Cr–Fe³⁺ substitution and the effects of order–disorder in the tetrahedral site. The spectral range at 500–620 cm^?1 region shows that there is a shift of modes toward lower values with the increase of the Mg-ferrite content. The peaks in the region at 200–500 cm^?1, when observed, show little or negligible Raman shift.     

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.     

Electronic absorption spectra of Fe2+ ions in oxygen-based rock-forming minerals at temperatures between 297 and 600 K

 Polarized electronic single crystal spectra of natural Fe²⁺ ion-bearing oxygen-based minerals, in which ferrous ions enter octahedral sites of different symmetry and distortion (olivine, cordierite, ortho- and clinopyroxene, amphibole), eightfold sites in garnet (almandine) and clinopyroxene (M2), and tetrahedral sites in spinel, were studied at temperatures from 300 to ca. 600 K. In the minerals studied, the spin-allowed bands of Fe²⁺ display rather variable temperature behaviour. In most cases, due to the thermal expansion of the Fe²⁺-bearing polyhedra, bands shift to lower energies upon increasing temperature, though there are some exceptions to this rule: in cases of other than sixfold octahedral or close to octahedral coordination, in almandine and spinel the bands shift to higher energies, which can be explained by an increase in distortions of the Fe²⁺-bearing polyhedra. Splitting of the excited ⁵ E _g-level of Fe²⁺ ions usually, but not always, increases with temperature, reflecting thermally induced increase in distortion of the Fe²⁺-bearing sites in the minerals studied. Integral intensities of the bands in question do not always obey the general rule, according to which intensity should increase with temperature, when the 3d ^N-centred site is centrosymmetric, or should remain unchanged when the 3d ^N site lacks an inversion centre. The experimental results show that the response of the characteristics of absorption bands such as width, intensity and energy caused by dd transitions of Fe²⁺ in oxygen-based minerals to increasing temperature is not always uniform and is at variance with expectation. This temperature dependence cannot be used directly to solve band assignment problems, as earlier proposed in the literature. Received: 22 December 1999 / Accepted: 30 October 2000