Optical absorption and electron spin resonance in blue and green natural beryl

A comparative study of blue and green beryl crystals (from the region of Governador Valadares, Minas Gerais, Brazil) using electron paramagnetic resonance (EPR) and optical absorption (OA) spectroscopy is reported. The EPR spectra show that Fe³⁺ in blue beryl occupies a substitutional Al³⁺ site and in green beryl is localized in the structural channels between two O₆ planes. On the other hand the infrared spectra show that the alkali content in the blue beryl is mostly at substitutional and/or interstitial sites and in green beryl is mostly in the structural channels. The OA spectra show two types of Fe²⁺. Thermal treatments above 200° C in green beryl cause the reduction of Fe³⁺ into Fe²⁺ accompanied by a change of color to blue. The blue beryl color does not change on heating. The kinetics of the thermal conversion of Fe³⁺ into Fe²⁺ is composed of two first order processes; the first one has an activation energy ΔE ₁=0.30 eV and the second one has an activation energy ΔE ₂=0.46 eV.     

An EPR study of Mn2+ and Fe3+ in dolomites

Electron paramagnetic resonance (EPR) measurements on dolomites from 9 different localities revealed contents of Mn²⁺ on two axial sites in all of them. The center with largerzero-field splitting (ZFS) was always present in much higher concentrations, except for a sample from Oberdorf it amounted to 95 percent or more of the total. This dolomite was the only one with a considerable content of Fe³⁺ on one axial site, almost certainly substituting for Mg²⁺. With X-ray irradiation the concentration of Fe³⁺ increased by about 30 percent showing that at least some of the divalent iron also substitutes for Mg. The ZFSs for Fe³⁺ and Mn²⁺ with larger ZFS increase with decreasing temperature in the same manner. The previous assignment of this Mn²⁺ to Mg sites is thus confirmed. An almost regular increase of the trigonal distortions at the divalent ions in different carbonates with increasing ionic radius is indicated by their crystal structure data. The very small ZFS for Mn²⁺ on Ca sites in dolomite must thus result from a strong local relaxation in the direction of a more regular octahedral arrangement. It is difficult to explain the different distribution ratios of Mn²⁺ on Ca and Mg sites with differences in growth and/or annealing temperatures alone. Thus different supply of Mg²⁺ and Ca²⁺ in the growth solutions may also contribute.     

Structure and physical property relations of Mn ilvaite

Structural and compositional data as well as ⁵⁷Fe Mössbauer parameters were determined on a natural Mn-rich monoclinic ilvaite crystal (ideal composition CaFe ₂ ²⁺ Fe³⁺Si₂O₈(OH)) which was used for electrical conductivity and thermopower measurements (part 2 of this paper). A zonar structure was found by electron microprobe analysis with a strong decrease in Mn concentration from the rim to the centre of the crystal in a plane perpendicular to the [001] direction. X-ray powder diffraction analysis of the most Mn-rich composition was performed. Mn²⁺ cations populate preferentially M2 sites of the ilvaite unit cell (space group P21/a), to a lower extent they reside on M1 and a reduced part is on Ca sites. The monoclinic angle was determined to β=90.178(4)°. The structural results are compared to literature data for other natural Mn-rich as well as low-impurity ilvaites; this concerns in particular the lattice b parameter and the undecided issue of the varying β angle. In the literature, the order parameter σ, which describes the varying degree of ordering of Fe²⁺–Fe³⁺ pairs on M11 and M12 sites in chains running parallel to the [001] direction, and structural defects are thought to be related to β. The interrelationship between β and σ with respect to a possible twin domain structure is discussed. Various ⁵⁷Fe Mössbauer spectra were recorded between 151 K and 327 K. Mössbauer parameters and Fe²⁺/Fe³⁺ concentration ratios were determined from the fits to the spectra. Fitting of subspectra was accomplished with the idea to find assignments of Fe²⁺ and Fe³⁺ doublets in agreement with X-ray results. The fraction of Mn²⁺ substituting Fe²⁺ on M1 sites could be estimated.     

Electron paramagnetic resonance study of iron(III) and manganese(II) in the glassy and crystalline environments of synthetic fayalite and tephroite

Crystals of the olivine minerals, tephroite (Mn₂SiO₄) and fayalite (Fe₂SiO₄) containing manganese(II) and iron (II and trace of III), respectively, were synthesized. Glasses were prepared from these crystalline materials by a splat-quench technique. Measurement of electron paramagnetic resonance (EPR) of all these powdered samples at room temperature show that the g-factors of Mn²⁺ in both glassy and crystalline environments (g_eff = 2.004) are the same, although the EPR linewidths (for glass, ΔH_pp = 200 G; for crystals ΔH_pp = 287 G) suggest less clustering of paramagnetic Mn²⁺ ions in the glass. Mn²⁺ probably occupies a distorted octahedral site in the tephroite crystal structure, although a four-fold coordination is suggested from other spectroscopic investigation on this glass. The EPR parameters of Fe³⁺ in synthetic fayalite glass (g_eff = 2.01 and 6.00; ΔH_pp=150 and 1375 G, respectively, for the high and low field resonances) and powdered crystals (g_eff = 3.31 and ΔH_pp = 900 G) indicated that Fe³⁺ ion in the crystals, is probably located in a distorted tetragonal site M2 and an axial environment has been proposed in the glassy system.     

The crystal chemistry of lithium and Fe3+ in synthetic orthopyroxene

Lithian ferrian enstatite with Li₂O = 1.39 wt% and Fe₂O₃ 7.54 wt% was synthesised in the (MgO–Li₂O–FeO–SiO₂–H₂O) system at P = 0.3 GPa, T = 1,000°C, fO₂ = +2 Pbca, and a = 18.2113(7), b = 8.8172(3), c = 5.2050(2) Å, V = 835.79(9) Å³. The composition of the orthopyroxene was determined combining EMP, LA-ICP-MS and single-crystal XRD analysis, yielding the unit formula ^M2(Mg_0.59Fe _0.21 ²⁺ Li_0.20) ^M1(Mg_0.74Fe _0.20 ³⁺ Fe _0.06 ²⁺ ) Si₂O₆. Structure refinements done on crystals obtained from synthesis runs with variable Mg-content show that the orthopyroxene is virtually constant in composition and hence in structure, whereas coexisting clinopyroxenes occurring both as individual grains or thin rims around the orthopyroxene crystals have variable amounts of Li, Fe³⁺ and Mg contents. Structure refinement shows that Li is ordered at the M2 site and Fe³⁺ is ordered at the M1 site of the orthopyroxene, whereas Mg (and Fe²⁺) distributes over both octahedral sites. The main geometrical variations observed for Li-rich samples are actually due to the presence of Fe³⁺, which affects significantly the geometry of the M1 site; changes in the geometry of the M2 site due to the lower coordination of Li are likely to affect both the degree and the kinetics of the non-convergent Fe²⁺-Mg ordering process in octahedral sites.     

Structural variation of babingtonite depending on cation distribution at the octahedral sites

Babingtonite, Ca₂Fe²⁺Fe³⁺[Si₅O₁₄(OH)] (Z?=?2, space group $ P\overline{1} $ ) from Yakuki mine (Japan), Grönsjöberget (Sweden), Kandivali Quarry (India), Baveno Quarry (Italy), Bråstad Mine (Norway), and Kouragahana (Japan), and manganbabingtonite, Ca₂(Mn²⁺, Fe²⁺)Fe³⁺[Si₅O₁₄(OH)], from Iron Cap mine (USA) were studied using electron-microprobe analysis (EMPA), ⁵⁷Fe Mössbauer analysis and single-crystal X-ray diffraction methods to determine the cation distribution at M1 and M2 and to analyze its effect on the crystal structure of babingtonite. Although all studied babingtonite crystals are relatively homogeneous, chemical zonation due to mainly Fe ? Mn substitution is observed in manganbabingtonite. Mössbauer spectra consist of two doublets with isomer shift (I.S.)?=?1.16–1.22 mm/s and quadrupole splitting (Q.S.)?=?2.33–2.50 mm/s and with I.S.?=?0.38–0.42 mm/s and Q.S.?=?0.82–0.90 mm/s, assigned to Fe²⁺ and Fe³⁺ at the M1 and M2 octahedral sites, respectively. The determined ratio of Fe²⁺/total Fe in manganbabingtonite (0.26) was smaller than that in the others (0.35–0.44) because of high Mn²⁺ content instead of Fe²⁺. The unit-cell parameters of babingtonite are a?=?7.466–7.478, b?=?11.624–11.642, c?=?6.681–6.690 Å, α?=?91.53–91.59, β?=?93.86–93.94, γ?=?104.20–104.34º, and V?=?560.2–562.3 Å³, and those of manganbabingtonite are a?=?7.4967(3), b?=?11.6632(4), c?=?6.7014(2) Å, α?=?91.602(2), β?=?93.989(2), γ?=?104.574(3)º, and V =565.09(5) ų. Structural refinements converged to R ₁ values of 1.64–3.16 %. The <M1-O> distance was lengthened due to the substitution of large octahedral cations such as Mn²⁺ for Fe²⁺. The increase of the M1-O8, M1-O8’ and M1-O13 lengths with mean ionic radii is slightly more pronounced than of the other M1-Oi lengths. The lengthened M1-O13 distance leads the positive correlation between Si5-O15-Si1 angle and M1-O13 distance. The increase of Si2-O3-Si1 and Si5-O12-Si4 angles due to the increase of mean ionic radius of M2 is also observed.     

Fe2+, Mg-distribution among non-equivalent structural sites M1 and M2 in natural olivines: an optical spectroscopy study

Analysis of E||X-polarized optical absorption spectra of natural olivines of various origin in the range of electronic spin-allowed dd-transitions of Fe²⁺ evidences that in some crystals, there is a weak ordering of Fe²⁺ as in M1, as in M2 structural sites. The samples of three different depth facies seem showing a vague tendency of lowering of k _D -values from spinel-pyroxene (Sp-Px) through graphite-pyrope (G-Py) to diamond-pyrope (D-Py) facies, but the statistics are too poor (24 samples only) to be certain of it. Weak relations between Mg, Fe²⁺-distribution and iron content were found for the samples of Sp-Px- and G-Py-facies, while there is practically no one for those of the deepest D-Py facie.     

The investigation of defects in shock-metamorphosed quartz

The shock-metamorphosed quartz exhibits thermal luminescence (TL) with maxima at 365 nm, 470 nm and 610–680 nm. By electron paramagnetic resonance (EPR) analysis E₁ type electron centers and hole centers have been found which originate from vacancies including those from the substitution of Al³⁺ and/or Fe³⁺, for Si⁴⁺. The EPR and TL spectra may be interpreted mainly in terms of vacancy type defects associated with dislocations in the crystal structure of quartz.     

Crystal-chemistry and cation ordering in the system diopside-jadeite: A detailed study by crystal structure refinement

The Nybö eclogite pod in Norway is characterized by a great variety of clinopyroxene compositions with Jd contents ranging from less than 5% up to nearly 80%, whilst Ac+Hd contents remain almost constant (mostly within 10±5%).Unconstrained X-ray structure refinement has been carried out on 16 pyroxene crystals (8 with C2/c and 8 with P2/n space group) from the Nybö eclogite, and also on one omphacite crystal (from Lago Mucrone in the Sesia-Lanzo Zone, Western Alps) which displays the highest degree of cation ordering yet described. The final discrepancy factors range from 0.014 to 0.029. The population of the sites has been determined on the basis of bond length considerations and of the results of the site occupancy refinement. Six of these crystals were subsequently analysed by electron microprobe.The tetrahedral sites are occupied by Si with negligible amounts of Al. Al, Mg, Fe³⁺ and Fe²⁺ occur at the octahedral sites; in the ordered P2/n crystals Al and Fe³⁺ are concentrated at the M11 site, whilst Mg and Fe²⁺ are concentrated and the M1 site. The eight-coordinated sites contain Ca and Na with negligible amounts of Fe and/or Mg. Ordering of Ca and Na takes place in the P2/n samples in such a way that in the most ordered crystal the M2 site contains almost exactly 0.75 Na+0.25 Ca and the M21 site 0.25 Na+0.75 Ca.Some geometrical features of the tetrahedra as well as of the octahedra (e.g. tetrahedral quadratic elongation and TILT angle) are not a simple linear function of composition, even when no change in space group occurs. The crystals evidently do not behave like a binary system of the two components, Di and Jd, but behave rather as if the composition Di_0.50 Jd_0.50 was a distinct end member.The boundaries between disordered and ordered phases in the Nybö pyroxenes fall at about 0.35 and 0.65 Jd/(Di+ Jd), in close agreement with the previous TEM investigations.The degree of order varies with composition following a bell-shaped curve: different coaxial bell-shaped curves can be drawn for crystals which have similar compositions but come from different metamorphic environments. The order vs composition diagrams may be useful for the interpretation of the P-T-t histories of the host rocks.     

Determination of Fe3+ and Fe2+ concentrations in feldspar by optical absorption and EPR spectroscopy

Ferrous and ferric iron concentrations in feldspars with low total iron content (<0.32 wt% total Fe) were determined from optical and electron paramagnetic resonance (EPR) spectra to better than ±15 percent of the amount present. Optical spectra indicate that Fe²⁺ occupies two distorted M-sites in plagioclases of intermediate structural state. The linear dependence of the Fe²⁺/Fe total ratio on An content demonstrates that Fe²⁺ substitutes for Ca (not Na) so that the number of Ca-sites is a principal factor in iron partitioning in plagioclase. EPR powder spectra show that the number of sites for Fe³⁺ depends on structural state rather than on plagioclase chemistry. The observed linear correspondence of EPR double-integrated intensities with optical peak areas shows that all Fe³⁺ is tetrahedrally coordinated in both plagioclase and disordered potassium feldspar. Microcline perthites show, in addition to tetrahedral Fe³⁺, a signal due to axially coordinated ferric iron, which we associate with formation of hematite inclusions.     

Crystal chemistry and reaction relations of piemontites and thulites from highly oxidized low grade metamorphic rocks at Vitali,Andros Island,Greece

Piemontite- and thulite-bearing assemblages from highly oxidized metapelitic and metacalcareous schists associated with braunite quartzites at Vitali, Andros island, Greece, were chemically investigated. The Mn-rich metasediments are intercalated in a series of metapelitic quartzose schists, marbles, and basic metavolcanites which were affected by a regional metamorphism of the highP/T type (T=400–500° C,P>9 kb) and a later Barrovian-type greenschist metamorphism (T=400–500° C,P～-5–6 kb). Texturally and chemically two generations of piemontite (I and II) can be distinguished which may show complex compositional zoning. Piemontite I coexisted at highP/T conditions with braunite, manganian phengite (alurgite), Mn³⁺-Mn²⁺-bearing Na-pyroxene (violan), carbonate, quartz, hollandite, and hematite. Zoned grains generally exhibit a decreasing Mn³⁺ and an increasing Fe³⁺ and Al content towards the rim. Chemical compositions of piemontite I range from 2.0 to 32.1 mole % Mn³⁺, 0 to 25.6 mole % Fe³⁺, and 60.2 to 81.2 mole % Al. Up to 12.5 mole % Ca on the A(2) site can be substituted by Sr. Piemontites formed in contact or close to braunite (±hematite) attained maximum (Mn³⁺+Fe³⁺)Al_?1 substitution corrresponding to about 33 mole % Mn³⁺+Fe³⁺ in lowiron compositions and up to about 39 mole % Mn³⁺+ Fe³⁺ at intermediate Fe³⁺/(Fe³⁺+Mn³⁺) ratios. Piemontite II which discontinuously overgrows piemontite I or occurs as separate grains may have been formed by greenschist facies decomposition of manganian Na-pyroxenes according to the reaction: (1) $$\begin{gathered} {\text{Mn}}^{{\text{3 + }}} - Mn^{2 + } - bearing omphacite/chloromelanite \hfill \\ + CO_2 + H_2 O + HCl \pm hermatite \hfill \\ = piemontite + tremolite + albite + chlorite \hfill \\ + calcite + quartz + NaCl \pm O_2 . \hfill \\ \end{gathered} $$ Thulites crystallized in coexistence with Al-rich piemontite II. All thulites analysed are low-Fe³⁺ manganian orthozoisites with Mn^tot～-Mn³⁺ substituting for Al on the M(3) site. Their compositions range from 2.9 to 7.2 mole % Mn³⁺, 0 to 1.2 mole % Fe³⁺, and 91.8 to 96.7 mole % Al. Piemontites II in thulite-bearing assemblages range from 5.8 to 15.9 mole % Mn³⁺, 0 to 3.7 mole % Fe³⁺, and 83.7 to 93.6 mole % Al. By contrast, piemontites II in thulite-free assemblages are similarly enriched in Mn³⁺ + Fe³⁺ — and partially in Sr²⁺ — as core compositions of piemontite I (21.1 to 29.6 mole % Mn³⁺, 2.0 to 16.5 mole % Fe³⁺, 60.6 to 68.4 mole % Al, 0 to 29.4 mole % Sr in the A(2) site). The analytical data presented in this paper document for the first time a continuous low-Fe³⁺ piemontite solid solution series from 5.8 to 32.1 mole % Mn³⁺. Aluminous piemontite II is enriched by about 3 mole % Mn³⁺+Fe³⁺ relative to coexisting thulite in Fe³⁺-poor samples and by about 6 mole % Mn³⁺+Fe³⁺ in more Fe³⁺-rich samples. Mineral pairs from different samples form a continuous compositional loop. Compositional shift of mineral pairs is attributed to the effect of a variable fluid composition at constantP _fluid andT on the continuous reaction: (2) $$\begin{gathered} piemontite + CO_2 \hfill \\ = thulite + calcite + quartz \hfill \\ + Mn^{2 + } Ca_{ - 1} [calcite] + H{_2} O + O{_2} \hfill \\ \end{gathered} $$ Further evidence for a variable \(x_{H_2 O} \) and/or \(f_{O_2 } \) possibly resulting from fluid infiltration and local buffering during the greenschist metamorphism is derived from the local decomposition of piemontite, braunite, and rutile to form spessartine, calcite, titanite, and hematite by the reactions: (3) $$\begin{gathered} piemontite + braunite + CO_2 \hfill \\ = sperssartine + calcite + quartz \pm hermatite \hfill \\ + H{_2} O + O{_2} \hfill \\ \end{gathered} $$ and more rarely: (4) $$\begin{gathered} piemontite + quartz + rutile + braunite \hfill \\ = spessartine + titanite + hematite + H{_2} O + O{_2} . \hfill \\ \end{gathered} $$      

Low temperature spectral studies of Mn3+-bearing andalusite and epidote type minerals in the range 30000–5000 cm−1

Polarized absorption spectra of natural piemontite (Ca_1.802Mn ²⁺_0.178 Mg_0.025) (Mn ³⁺_0.829 Fe ³⁺_0.346 Al_1.825) [(Si_2.992Al_0.008) O₁₂OH], viridine (Al_1.945Mn ³⁺_0.033 Fe ³⁺_0.063 Mg_0.003) [O|Si_0.970 O₄], and kanonaite (Al_1.291Mn ³⁺_0.682 Fe ³⁺_0.019 ) [O|Si_1.006 O₄] were measured at 295 and ca. 100 K. For piemontite, lowering the temperature resulted in a sharpening of broad bands in the 10 000–25 000 cm⁻¹ region supporting their assignment to single ion Mn³⁺ in M3 non-centrosymmetric sites.

Alternatively, in kanonaite, temperature behaviour pointed to a slightly stronger influence of vibronic coupling on strong bands near 16 000 and 22 000 cm⁻¹, which supported an interpretation of Mn³⁺ in nearly centrosymmetric M1 sites. Measurements at ca. 100 K show pronounced fine structure in the viridine spectra which is attributed to Fe³⁺. The ɛ values for Mn³⁺ spin-allowed bands in the three minerals lie in the range 18 to 227 [1·g-atom⁻¹·cm⁻¹].

For the same band and polarisation, ɛ values in Mn³⁺-bearing andalusite-type minerals viridine and kanonaite are the same, which indicates an absence of strong magnetic coupling effects between Mn³⁺ ions in the andalusite type structure down to ca. 100 K.

In silicates, the high ɛ values for Mn³⁺ spin-allowed bands, in comparison to those obtained for Fe²⁺ spin-allowed bands from sites of “similar distortion”, is attributed to a higher degree of covalency in the Mn³⁺-O bonds compared to the Fe²⁺-O bonds, as a result of the higher valence state of manganese.

     

57Fe mössbauer study of clinopyroxenes in the join CaFe3+ AlSiO6 - CaTiAl2O6

Synthetic clinopyroxenes of compositions between CaFe³⁺AlSiO₆ and CaFe _0.85 ³⁺ Ti_0.15Al_1.15Si_0.85O₆ have been studied by ⁵⁷Fe Mössbauer spectroscopy. The spectra consist of two doublets assigned to Fe³⁺ in M1 and T sites. From the area ratios of the doublets the site occupancies of Fe³⁺ and Al were determined. Si decreases from 1.00 to 0.85 and Al+Fe³⁺ increases from 1.00 to 1.15 per formula unit with increasing CaTiAl₂O₆ component of the clinopyroxene. The atomic ratio of Fe³⁺(T)/Fe³⁺(total) is 0.11–0.16; 4.5–7.5 percent of the T sites are occupied by Fe³⁺. Thus the presence of Si-O-Fe³⁺, Al-O-Fe³⁺, and Fe³⁺-O-Fe³⁺ bonds is expected in addition to Si-O-Si, Si-O-Al and Al-O-Al bonds. However, the possibility of the former bonds being present would be small, because the amount of Fe³⁺(T) is far less than that of Si and Al. The isomer shift of Fe³⁺(T) is one of the largest in the values found previously for Fe³⁺(T) in silicates. It increases with increasing CaTiAl₂O₆ component and seems to be correlated to the ionic character of the cation — anion bonds calculated from electronegativity. The quadrupole splittings of Fe³⁺(M1) and Fe³⁺(T) decrease with the substitution of Fe³⁺?Ti⁴⁺ in the M1 and of Si?Al in the T sites.     

Study of structural and valence state of Cr and Fe in chrysoberyl and alexandrite with EPR and M?ssbauer spectroscopy

Data on the structural and valence distribution of Cr and Fe in chrysoberyl and in alexandrite, its gem variety, are given. It is shown that the Cr³⁺ line in the natural Ural and Tanzania samples is the strongest in the M1 site and for the synthetic stones, in the M2 site. During the annealing of the alexandrite crystals, Cr³⁺ passes from the smaller M1 site into the larger M2 site. The M?ssbauer spectroscopy quantitatively determined the distribution of different valence Fe ions. The various proportions of both Fe²⁺ and Fe³⁺ ions isomorphically entering the octahedral sites in the BeAl₂O₄ crystal structure were established.     

Temperature-dependent Fe2+–Mn2+ order–disorder behaviour in amphiboles

The partitioning of Fe and Mn between the large M(4) site and the octahedral sites, M(1,2,3) in the amphibole structure has been investigated in two natural manganogrunerites of compositions Ca_0.1Mn_1.9 Mg_1.25Fe²⁺ _3.56Fe³⁺ _0.38Si_7.81O₂₂(OH)₂ and Ca_0.24Mn_1.57 Mg_2.27 Fe²⁺ _2.76Fe³⁺ _0.32Si_7.84O₂₂(OH)₂. The long-range cation distribution in the two samples has been elucidated by in situ neutron powder diffraction revealing that Mn is preferentially ordered onto M(4) ? M(2) >M(1) >M(3) in both samples. Partitioning of Mn from M(4) into the octahedral sites begins at 350 °C, with site exchange energies of ?16.6 kJ mol^?1 and ?14.9 kJ mol^?1, in samples containing 1.90 and 1.57 Mn apfu, respectively. Mössbauer and infrared spectroscopy have been used to study the samples at room temperature, and Mössbauer data agree well with the diffraction results, confirming that high-temperature cation distributions are retained during cooling. The fine structure in the hydroxyl-stretching region of the IR absorption spectra has been used to discuss qualitatively the site occupancies of the coordinating M(1)M(3)M(1) triplet, linked by O(3). On the basis of such modelling, we conclude that a degree of local clustering is present in both samples.     

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.     

Mössbauer and molecular orbital study of chlorites

The different Fe²⁺ lattice sites in iron-rich chlorites have been characterized by Mössbauer spectroscopy and molecular orbital calculations in local density approximation. The Mössbauer measurements were recorded at 77?K within a small velocity range (±3.5?mm?s^?1) to provide high energy resolution. Additionally, measurements were recorded in a wider velocity range (±10.5?mm?s^?1) at temperatures of 140, 200, and 250?K in an applied field (7?T) parallel to the γ-beam. The zero-field spectra were analyzed with discrete Lorentzian-shaped quadrupole doublets to account for the Fe²⁺ sites M1, M2, and M3 and with a quadrupole distribution for Fe³⁺ sites. Such a procedure is justified by the results obtained from MO calculations, which reveal that different anion (OH^?) distributions in the first coordination sphere of M1, M2, and M3 positions have more influence on the Fe²⁺ quadrupole splitting than cationic disorder. The spectra recorded in applied field were analyzed in the spin-Hamiltonian approximation, yielding a negative sign for the electric field gradient (efg) of Fe²⁺ in the M1, M2, and M3 positions. The results of the MO calculations are in quantitative agreement with experiment and reveal that differences in the quadrupole splittings (ΔE _Q ), their temperature dependence and in the isomer shifts (δ) of Fe²⁺ in M1, M2, and M3 positions can theoretically by justified. Therefore, the combined Mössbauer and MO investigation shows that the three Fe²⁺ lattice sites in the chlorites investigated here can be discriminated according to their ΔE _Q -δ parameter pairs. With the calculated average iron-oxygen bond strength, the MO study provides an explanation for the observed trend that the population of the three lattice sites by Fe²⁺ increases according to the relation M1?相似文献   

Polarized electronic absorption spectra of synthetic (Mg,Fe)-orthopyroxenes,ferrosilite and Fe3+-bearing ferrosilite

The assignment of spin-allowed Fe²⁺-bands in orthopyroxene electronic absorption spectra is revised by studying synthetic bronzite (Mg_0.8 Fe_0.2)₂Si₂O₆, hypersthene (Mg_0.5 Fe_0.5)₂Si₂O₆ and ferrosilite (Fe₂Si₂O₆). Reheating of bronzite and hypersthene single crystals causes a redistribution of the Fe²⁺-ions over the M1 and M2 octahedra, which was determined by Mössbauer spectroscopy and correlated to the intensity change of the spin-allowed Fe²⁺ d-d bands in the polarized absorption spectra. The 11000 cm^-1 band is caused by Fe²⁺ in M1 (⁵B_2g→⁵A_1g) and Fe²⁺ in M2 (⁵A₁→⁵A₁), the 8500 cm^-1 band by Fe²⁺ in M1 (⁵B_2g→⁵B_1g) and the 5000 cm^-1 band by Fe²⁺ in M2 octahedra (⁵A₁→⁵B₁). The Fe²⁺-Fe³⁺ charge transfer band is identified at 12500cm^-1 in the spectra of synthetic Fe³⁺ -Al bearing ferrosilite. This band shows a strong γ-polarization and therefore is caused by Fe²⁺ -Fe³⁺-ions in edge-sharing octahedra.     

High pressure single-crystal synthesis, structure and compressibility of the garnet Mn2+ 3Mn3+ 2[SiO4]3

Single crystals of the garnet Mn²⁺ ₃Mn³⁺ ₂[SiO₄]₃ and coesite were synthesised from MnO₂-SiO₂ oxide mixtures at 1000°C and 9 GPa in a multianvil press. The crystal structure of the garnet [space group Ia3¯d, a=11.801(2) Å] was refined at room temperature and 100 K from single-crystal X-ray data to R1=2.36% and R1=2.71%, respectively. In contrast to tetragonal Ca₃Mn³⁺ ₂[GeO₄]₃ (space group I4₁/a), the high-pressure garnet is cubic and does not display an ordered Jahn-Teller distortion of octahedral Mn³⁺. A disordered Jahn-Teller distortion either dynamic or static is evidenced by unusual high anisotropic displacement parameters. The room temperature structure is characterised by following bond lengths: Si-O=1.636(4) Å (tetrahedron), Mn³⁺-O=1.995 (4) Å (octahedron), Mn²⁺-O=2.280(5) and 2.409(4) Å (dodecahedron). The cubic structure was preserved upon cooling to 100 K [a=11.788(2) Å] and upon compressing up to 11.8 GPa in a diamond-anvil cell. Pressure variation of the unit cell parameter expressed by a third-order Birch-Murnaghan equation of state led to a bulk modulus K ₀=151.6(8) GPa and its pressure derivatives K′=6.38(19). The peak positions of the Raman spectrum recorded for Mn²⁺ ₃Mn³⁺ ₂[SiO₄]₃ were assigned based on a calderite Mn²⁺ ₃Fe³⁺ ₂[SiO₄]₃ model extrapolated from andradite and grossular literature data.     

Crystal Structure and Chemical Composition of Ludwigite from Vranovac Ore Deposit (Boranja Mountain,Serbia)

The crystal structure of ludwigite from Vranovac ore deposit (Boranja Mt., Serbia) was refined using the X-ray powder diffraction (XRPD) Rietveld method in the space group Pbam to a final RB=7.45% and RF=5.26%. It has the unit cell dimensions of: a=9.2515(2) ?; b=12.3109(2) ?; c=3.03712(7) ?; and V=345.91(1) ?3. The calculated distances and angles are mostly in good agreement with the Mg2+-Fe2+ substitutions across the M(1) and M(3) sites, as well as with the Fe3+-Al3+ replacement in the M(4) site. However, the mean observed M(2)-O distance is considerably shorter than prescribed, due to a slight increase of the Fe3+ content in the M(2) site. Such replacement was compensated by slight increase of the Fe2+ content in the M(4) site, resulting in the (Mg1.48Fe2+0.46Fe3+0.05Mn0.02)2.01(Fe3+0.94Fe2+0.04Al0.02)1.00B1.00O5 composition. The formation temperature was estimated to be about 500–600°C. The influences of the various chemical compositions to the crystallographic parameters, M-O distances, M(3) and M(4) sites shift, distortion parameters and estimated valences, were also studied and compared with other reference samples.