Valent state and coordination of cobalt Ions in beryl and chrysoberyl crystals

We have studied the polarized optical absorption and EPR spectra of Co-doped beryls grown by hydrothermal, flux, and gas-transport methods, and chrysoberyl grown by the Czochralski method. In beryls three groups of bands, belonging to three various Co centers, were distinguished by analysis of the absorption band intensities. The first group, bands with maxima at 22 220 (E c), 17 730 (E c), and 9090 (E c), 7520 (E c) cm^–1 are due to Co²⁺ in octahedral site of Al³⁺. The second group is bands at 18 940, 18 250, 17 700 (E c), 18 300, 17 700, 17 000 (E c) and 8830 (E c), 7350 (E c) cm^–1 and 5320 (E c), 3880 (E c) cm^–1, which are caused by Co²⁺ in tetrahedral site of Be²⁺. A weak wide band in flux and gas-transport beryl in the region of 12 500–8300 cm^–1 (E , c) is related to Co³⁺ in octahedral Al³⁺ site. In hydrothermal beryl, bands 13 200 (E c), 10 900 (E c), and 8500 (E c) cm^–1 are caused by an uncontrolled impurity of Cu²⁺ ions. For Co-doped chrysoberyl one type of center of Co has been established: Co²⁺ in the octahedral site of Al³⁺. In the approximation of the trigonal field with regard to Trees correction, the energy levels of Co²⁺ have been calculated in octahedral and tetrahedral coordination. There is good agreement between the obtained experimental and calculated data. The polarization dependence of the optical absorption bands is explained well in terms of the spin-orbit interaction.     

The single-crystal,polarized-light,FTIR spectrum of stoppaniite,the Fe analogue of beryl

We report here a single-crystal polarized-light study of stoppaniite, ideally (Fe,Al,Mg)₄(Be₆Si₁₂O₃₆)(H₂O)₂(Na,□), from Capranica (Viterbo). Polarized-light FTIR spectra were collected on an oriented (hk0) section, doubly polished to 15 μm. The spectrum shows two main bands at 3,660 and 3,595 cm⁻¹; the former is strongly polarized for E ⊥c, while the latter is polarized for E //c. A sharp and very intense band at 1,620 cm⁻¹, plus minor features at 4,000 and 3,228 cm⁻¹ are also polarized for E //c. On the basis of literature data and considering the pleochroic behavior of the absorptions, the 3,660 cm⁻¹ band is assigned to the ν₃ stretching mode and the 1,620 cm⁻¹ (associated with an overtone 2*ν₂ at 3,230 cm⁻¹) band to the ν₂ bending mode of “type II” water molecules within the structural channels of the studied beryl. The sharp band at 3,595 cm⁻¹ is not associated with a corresponding ν₂ bending mode; thus it is assigned to the stretching vibration of O–H groups in the sample. The minor 4,000 cm⁻¹ feature can be assigned to the combination of the O–H bond parallel to c with a low-frequency metal-oxygen mode such as the Na–O stretching mode. The present results suggest that the interpretation of the FTIR spectrum of Na-rich beryl needs to be carefully reconsidered.     

Hydroxyl in mantle olivine xenocrysts from the Udachnaya kimberlite pipe

The incorporation of hydrogen in mantle olivine xenocrysts from the Udachnaya kimberlite pipe was investigated by Fourier-transform infrared spectroscopy and secondary ion mass spectrometry (SIMS). IR spectra were collected in the OH stretching region on oriented single crystals using a conventional IR source at ambient conditions and in situ at temperatures down to −180°C as well as with IR synchrotron radiation. The IR spectra of the samples are complex containing more than 20 strongly polarized OH bands in the range 3,730–3,330 cm⁻¹. Bands at high energies (3,730–3,670 cm⁻¹) were assigned to inclusions of serpentine, talc and the 10 Å phase. All other bands are believed to be intrinsic to olivine. The corresponding point defects are (a) associated with vacant Si sites (3,607 cm⁻¹ E || a, 3,597 E || a, 3,571 cm⁻¹ E || c, 3,567 E || c, and 3,556 E || b), and (b) with vacant M1 sites (most of the bands polarized parallel to a). From the pleochroic behavior and position of the OH bands associated with the vacant M1 sites, we propose two types of hydrogen—one bonded to O1 and another to O2, so that both OH vectors are strongly aligned parallel to a. The O2–H groups may be responsible for the OH bands at higher wavenumbers than those for the O1–H groups. The multiplicity of the corresponding OH bands in the spectra can be explained by different chemical environments and by slightly different distortions of the M1 sites in these high-pressure olivines. Four samples were investigated by SIMS. The calculated integral molar absorption coefficient using the IR and SIMS results of 37,500±5,000 L mol H₂O cm⁻² is within the uncertainties slightly higher than the value determined by Bell et al. (J Geophys Res 108(B2):2105–2113, 2003) (28,450±1,830 L mol H₂O cm⁻²). The reason for the difference is the different distributions of the absorption intensity of the spectra of both studies (mean wavenumber 3,548 vs. 3,570 cm⁻¹). Olivine samples with a mean wavenumber of about 3,548 cm⁻¹ should be quantified with the absorption coefficient as determined in this study; those containing more bands at higher wavenumber (mean wavenumber 3,570 cm⁻¹) should be quantified using the value determined by Bell et al. (J Geophys Res 108(B2):2105–2113, 2003).

Optical spectroscopic study of synthetic NaScSi<Subscript>2</Subscript>O<Subscript>6</Subscript>–CaNiSi<Subscript>2</Subscript>O<Subscript>6</Subscript> pyroxenes at normal and high pressures

Six synthetic NaScSi₂O₆–CaNiSi₂O₆ pyroxenes were studied by optical absorption spectroscopy. Five of them of intermediate (Na_1−x , Ca _x )(Sc_1−x , Ni _x )Si₂O₆ compositions show spectra typical of Ni²⁺ in octahedral coordination, more precise Ni²⁺ at the M1 site of the pyroxene structure. The common feature of all spectra is three broad absorption bands with maxima around 8,000, 13,000 and 24,000 cm⁻¹ assigned to ³ A _2g → ³ T _2g, ³ A _2g → ³ T _1g and →³ T _1g (³ P) electronic spin-allowed transitions of ^VINi²⁺. A weak narrow peak at ∼14,400 cm⁻¹ is assigned to the spin-forbidden ³ A _2g → ¹ T _2g (¹ D) transition of Ni²⁺. Under pressure the spin-allowed bands shift to higher energies and change in intensity. The octahedral compression modulus, calculated from the shift of the ³ A _2g → ³ T _2g band in the (Na_0.7Ca_0.3)(Sc_0.7Ni_0.3)Si₂O₆ pyroxene is evaluated as 85±20 GPa. The Racah parameter B of Ni²⁺(M1) is found gradually changing from ∼919 cm⁻¹ at ambient pressure to ∼890 cm⁻¹ at 6.18 GPa. The Ni end-member pyroxene [(Ca_0.93 Ni_0.07)NiSi₂O₆] has a spectrum different from all others. In addition to the above mentioned bands of Ni²⁺(M1) it displays several new relatively intense and broad extra bands, which were attributed to electronic transitions of Ni²⁺ at the M2 site. In difference to CaO₈ polyhedron geometry of an eightfold coordination, Ni²⁺(M2)O₈ polyhedra are assumed to be relatively large distorted octahedra. Due to different distortions and different compressibilities of the M1 and M2 sites the Ni²⁺(M1)- and Ni²⁺(M2)-bands display rather different pressure-induced behaviors, becoming more resolved in the high-pressure spectra than in that measured at atmospheric pressure. The octahedral compression modulus of Ni²⁺(M1) in this end-member pyroxene is evaluated as 150 ± 25 GPa, which is noticeably larger than in Ni_0.3 pyroxene. This is due to a smaller size and, thus, a stiffer character of Ni²⁺(M1)O₆ octahedron in the (Ca_0.93Ni_0.07)NiSi₂O₆ pyroxene compared to (Na_0.7Ca_0.3)(Sc_0.7Ni_0.3)Si₂O₆.

Variation of infrared absorption spectra in the system Bi2Al4−x Fe x O9 (x = 0–4), structurally related to mullite

The crystal structure of Bi₂Al_4−x Fe _x O₉ compounds (x = 0–4) has striking similarities with the crystal structure of mullite. A complete substitution of Al by Fe³⁺ in both octahedral and tetrahedral sites is a particular structural feature. The infrared (IR) spectra of the Bi₂M₄O₉ compounds (M = Al, Fe³⁺) are characterised by three band groups with band maxima in the 900–800, 800–600 and 600–400 cm⁻¹ region. Based on the spectroscopic results obtained from mullite-type phases, the present study focuses on the composition-dependent analysis of the 900–800 cm⁻¹ band group, which is assigned to Al(Fe³⁺)–O stretching vibrations of the corner-sharing MO₄ tetrahedra. The Bi₂Al₄O₉ and Bi₂Fe₄O₉ endmembers display single bands with maxima centred at 922 and 812 cm⁻¹, respectively. Intermediate Bi₂Al_4−x Fe _x O₉ compounds exhibit a distinct splitting into three relatively sharp bands, which is interpreted in terms of ordering effects within the tetrahedral pairs. Thereby the high-energy component band of the band triplet relates to Al–O–Al conjunctions and the low-energy component band to Fe–O–Fe conjunctions. The intermediate band is assigned to stretching vibrations of Al–O–Fe or Fe–O–Al configurations of the corner-sharing tetrahedral pairs. Bands in the 800–600 cm⁻¹ range are assigned to low-energy stretching vibrations of the MO₄ tetrahedra and to M–O–M bending vibrations of the tetrahedral pairs. Absorptions in the 600–400 cm⁻¹ range are essentially determined by M–O stretching modes of the M cations in octahedral coordination.     

Channel constituents in synthetic beryl: ammonium

 The infrared spectra and electron paramagnetic resonance (EPR) of channel constituents in beryls synthesized hydrothermally in the presence of NH₄Cl were investigated. Two forms of ammonium ion were observed to be incorporated into the c -channel. IR-spectra show the double band at 3295 and 3232 cm⁻¹ and two broad bands between 2600 and 3000 cm⁻¹ which were assigned to the NH₃ molecule and NH₄ ⁺ ion, respectively. Similar N–H stretching vibrations are also observed in Regency hydrothermal synthetic beryls and can be used to separate these synthetic beryls from their natural counterparts. After γ-irradiation of hydrothermally grown samples at 77 K, the EPR of the NH₃ ⁺(I) radical was observed. The NH₃ ⁺(II) radical replaces the NH₃ ⁺(I) radical when the sample is heated to room temperature. Both the NH₃ molecule and the NH₃ ⁺ radical have their C₃ symmetry axes perpendicular to the crystal c-axis. The spin Hamiltonian parameters of the NH₃ ⁺(I) are axial-symmetric due to the rapid rotation of the radical about the c-axis. The NH₃ ⁺(II) radical has a low symmetry and shows a hindered rotation because of its shift from the c-axis position and an interaction with the proton in the near neighbourhood. Possible models for the paramagnetic centres are discussed. Received: 16 May 2000 / Accepted: 5 July 2001     

On the mechanisms for H and Al incorporation in stishovite

The solubility and incorporation mechanisms of hydrogen in synthetic stishovite as a function of Al₂O₃ content have been investigated. Mechanisms for H incorporation in stishovite are more complex than previously thought. Most H in stishovite is incorporated via the Smyth et al. (Am Mineral 80:454–456, 1995) model, where H docks close to one of the shared O–O edges, giving rise to an OH stretching band in infrared (IR) spectra at 3,111–3,117 cm⁻¹. However, careful examination of IR spectra from Al-stishovite reveals the presence of an additional OH band at 3,157–3,170 cm⁻¹. All H is present on one site, with interstitial H both coupled to Al³⁺ substitutional defects on adjacent octahedral (Si⁴⁺) sites, and decoupled from other defects, giving rise to two distinct absorption bands. Trends in IR data as a function of composition are consistent with a change in Al incorporation mechanism in stishovite, with Al³⁺ substitution for Si⁴⁺ charge-balanced by oxygen vacancies at low bulk Al₂O₃ contents, and coupled substitution of Al³⁺ onto octahedral (Si⁴⁺) and interstitial sites at high bulk Al₂O₃ contents. Trends in OH stretching frequencies as a function of Al₂O₃ content suggest that any such change in Al incorporation mechanism could alter the effect that Al incorporation has on the compressibility of stishovite, as noted by Ono et al. (Am Mineral 87:1486–1489, 2002).     

Temperature dependence of the polarized electronic absorption spectra of olivines. Part I – fayalite

 Polarized electronic absorption spectra of orthorhombic fayalite, Fe₂SiO₄, [E || a(|| Z),E || b(|| X), E || c(|| Y)], space group Pbnm, have been studied in the temperature range 293 ≤T/K ≤ 1273. The spectra were analysed into component bands originating from spin-allowed dd transitions of iron(II) at the different sites, M1 and M2, in the structure. The assignments of bands, made on the basis of the polarization dependence of the spectra and considerations of transition energies, were confirmed by the analysis of the temperature-dependent spectra. The temperature dependencies of integral intensities, half band widths and energy positions of absorptions bands caused by Fe²⁺ on the different octahedral sites, M1 and M2, were evaluated for the individual transitions. Independent of the site symmetry, absorption bands shift to lower energies and half band widths increase on rising temperature. The temperature dependence of band intensities depends on site symmetry. The integral intensities are found to increase with temperature for the transition metal ion on a centrosymmetric site, or remain constant when the site is missing an inversion centre. This is consistent with the general conclusion of Taran et al. (1994). Received: 11 October 2001 / Accepted: 17 January 2002     

Electronic absorption by Ti3+ ions and electron delocalization in synthetic blue rutile

Polarized absorption spectra, σ and π, in the spectral range 30000–400 cm⁻¹ (3.71–0.05 eV) were obtained on crystal slabs // [001] of deep blue rutile at various temperatures from 88 to 773 K. The rutile crystals were grown in Pt-capsules from carefully dried 99.999% TiO₂ rutile powder at 50 kbar/1500 °C using graphite heating cells in a belt-type apparatus. Impurities were below the detection limits of the electron microprobe (about 0.005 wt% for elements with Z≥13). The spectra are characterized by an unpolarized absorption edge at 24300 cm⁻¹, two weak and relatively narrow (Δν_1/2≈3500–4000 cm⁻¹), slightly σ-polarized bands ν₁ at 23500 cm⁻¹ and ν₂ at 18500 cm⁻¹, and a complex, strong band system in the NIR (near infra red) with sharp weak peaks in the region of the OH stretching fundamentals superimposed on the NIR system in the σ-spectra. The NIR band system and the UV edge produce an absorption minimum in both spectra, σ and π, at 21000 cm⁻¹, i.e. in the blue, which explains the colour of the crystals. Bands ν₁ and ν₂ are assigned to dd transitions to the Jahn-Teller split upper E_g state of octahedral Ti³⁺. The NIR band system can be fitted as a sum of three components. Two of them are partly π-polarized, nearly Gaussian bands, both with large half widths 6000–7000 cm⁻¹, ν₃ at 12000 cm^–1 and the most intense ν₄ at 6500 cm⁻¹. The third NIR band ν₅ of a mixed Lorentz-Gaussian shape with a maximum at 3000 cm⁻¹ forms a shoulder on the low-energy wing of ν₄. Energy positions, half band widths and temperature behaviour of these bands are consistent with a small polaron type of Ti³⁺Ti⁴⁺ charge transfer (CT). Polarization dependence of CT bands can be explained on the basis of the structural model of defect rutile by Bursill and Blanchin (1983) involving interstitial titanium. Two OH bands at 3322 and 3279 cm⁻¹ in σ-spectra show different stability during annealing, indicating two different positions of proton in the rutile structure, one of them probably connected with Ti³⁺ impurity. Total water concentration in blue rutile determined by IR spectroscopy is 0.10 wt-% OH. The EPR spectra measured in the temperature interval 20–295 K show the presence of an electron centre at temperatures above 100 K and Ti³⁺ ions in more than one structural position, but predominantly in compressed interstitial octahedral sites, at lower temperatures. These results are in good agreement with the conclusions based on the electronic absorption data. Received: 24 March 1997 / Revised, accepted: 14 October 1997     

Thermal decomposition of Ferrian chamosite: an infrared emission spectroscopic study

The thermal behaviour of ripidolite, an iron-rich chlorite, has been studied in situ by infrared emission spectroscopy up to 800 °C. The more di,trioctahedral nature due to significant amounts of Fe³⁺ is reflected, in addition to the two bands around 3420 and 3560 cm⁻¹, by an extra band around 3345 cm⁻¹. This extra band is absent in pure dioctahedral chlorites without Fe³⁺. These bands have been assigned to (AlAl)O-OH, (SiAl)O-OH and (SiSi)O-OH stretching modes with increasing frequencies. The bands disappear upon dehydroxylation around 650 °C. A similar behaviour is observed for the corresponding libration modes around 716, 759 and 802 cm⁻¹. The stretching and bending modes of the inner-OH of the octahedral sheet in the 2:1 clay-like layer are observed around 3645, 943 and 904 cm⁻¹. Although the bands decrease in intensity, they remain present up to 800 °C as dehydroxylation of the octahedral sheet is not yet complete at this temperature. The presence of two bending modes is explained as being due to a differentiation between Mg-OH and Fe-OH modes. At 650 °C a new sharp band is observed around 502 cm⁻¹ assigned to a (Fe,Mg)-O-Al bending mode caused by the formation of a spinel-like interlayer phase after dehydroxylation. Received: 4 June 1999 / Accepted: 6 August 1999     

Optical absorption of electronic Fe–Ti charge-transfer transition in natural andalusite: the thermal stability of the charge-transfer band

Differently colored natural Brazilian andalusite crystals heat-treated under reducing and oxidizing conditions were analyzed by optical spectroscopy. The intensity of a broad intense band at around 20,500 cm⁻¹ in the optical absorption spectra of all color zones of the sample is proportional to the product of Ti- and Fe-concentrations and herewith proves its attribution to electronic Fe²⁺/Ti⁴⁺ IVCT transition. The band is strictly E||c-polarized, causing an intense red coloration of the samples in this polarization. The polarization of the Fe²⁺/Ti⁴⁺ IVCT band in andalusite, E||c, shows that the electronic charge-transfer process takes place in Al–O octahedral groups that share edges with neighbors on either side, forming chains parallel to the c-axis of the andalusite structure. Under thermal treatments in air, the first noticeable change is some intensification of the band at 800°C. However, at higher temperatures its intensity decreases until it vanishes at 1,000°C in lightly colored zones and 1,100°C in darkly colored ones. Under annealing in reducing conditions at 700 and 800°C, the band also slightly increases and maintains its intensity at treatments at higher temperatures up to 1,000°C. These results demonstrate that weakening and disappearance of the Fe²⁺/Ti⁴⁺ IVCT band in spectra of andalusite under annealing in air is caused by oxidization of Fe²⁺ to Fe³⁺ in IVCT Fe²⁺/Ti⁴⁺-pairs. Some intensification of the band at 800°C is, most probably, due to thermally induced diffusion of Fe²⁺ and Ti⁴⁺ in the structure that leads to aggregation of “isolated” Ti⁴⁺ and Fe²⁺ ions into Fe²⁺–Ti⁴⁺-pairs. At higher temperatures, the competing process of Fe²⁺ → Fe³⁺ oxidation overcomes such “coupling” and the band continues to decrease. The different thermal stability of the band in lightly and darkly colored zones of the samples evidence some self-stabilization over an interaction of Fe²⁺/Ti⁴⁺-pairs involved in IVCT process.     

Temperature dependence of the polarized electronic absorption spectra of olivines. Part II—Cobalt-containing olivines

Polarized electronic absorption spectra of single crystalline Co₂[SiO₄] and (Co_0.64Mg_0.36)₂[SiO₄] (E|| a (|| Z), E || b (|| X), E || c (|| Y)) have been studied in the temperature range 293 T/K 1273. The three polarized spectra show a total of 15 bands. Five bands are caused by spin-allowed transitions in Co²⁺ ions at M1 sites which appear in all polarization directions. Seven polarization-dependent bands can be ascribed to spin-allowed transitions in Co²⁺ ions at M2 sites and three bands may be assigned to spin-forbidden transitions. The assignment of bands due to Co²⁺ ions at M1 and M2 sites has been made on the basis of transition energies and intensity ratios. Further arguments have been derived from the comparison of spectra of crystals with different cobalt content, from the analysis of the polarization dependence of the spectra, and from the evolution of band intensities with temperature.     

Origin of the color in cobalt-doped quartz

Synthetic Co-doped quartz was grown hydrothermally in steel autoclaves at the Technological Center of Minas Gerais (CETEC), Brazil. The quartz samples, originally yellow in the as-grown state acquired blue coloration after prolonged heat treatment times at 500°C near the alpha–beta transition temperature. UV–VIS–NIR absorption spectroscopy shows the characteristic spectra of Co³⁺ before heat treatment. After heat treatment, the optical absorption spectrum is dominated by two split-triplet bands the first in the near infrared region centered at about 6,700 cm⁻¹ (1,490 nm) and the second in the visible spectral range at about 16,900 cm⁻¹ (590 nm). Both split-triplet bands are typical for Co²⁺ ions in tetrahedral coordination environments. From the absence of electron paramagnetic resonance (EPR) spectra, we conclude that the Co²⁺ found in the optical absorption spectra of the blue quartz is not due to an isolated structural site in the quartz lattice. Instead, the blue color is associated with electronic transitions of Co²⁺ in small inclusions in which the Co site has tetrahedral symmetry. The non-observation of polarization-depend optical absorption spectra is also in agreement with this model. The results for Co²⁺ in quartz are different from Co-bearing spinel and staurolite and other silicates like orthopyroxene, olivine, and beryls. The formation process of the color center is discussed.     

Electronic absorption and luminescence spectroscopic studies of kyanite single crystals: differentiation between excitation of FeTi charge transfer and Cr3+ dd transitions

A selected set of five different kyanite samples was analysed by electron microprobe and found to contain chromium between <0.001 and 0.055 per formula unit (pfu). Polarized electronic absorption spectroscopy on oriented single crystals, R₁, R₂-sharp line luminescence and spectra of excitation of λ₃- and λ₄-components of R₁-line of Cr³⁺-emission had the following results: (1) The Fe²⁺–Ti⁴⁺ charge transfer in c-parallel chains of edge connected M(1) and M(2) octahedra shows up in the electronic absorption spectra as an almost exclusively c(||Z′)-polarized, very strong and broad band at 16000 cm⁻¹ if <, in this case the only band in the spectrum, and at an invariably lower energy of 15400 cm⁻¹ in crystals with  ≥ . The energy difference is explained by an expansion of the O_f–O_k, and O_b–O_m edges, by which the M(1) and M(2) octahedra are interconnected (Burnham 1963), when Cr³⁺ substitutes for Al compared to the chromium-free case. (2) The Cr³⁺ is proven in two greatly differing crystal fields a and b, giving rise to two sets of bands, derived from the well known dd transitions of Cr^{3+ 4}A_2g→⁴T_2g(F)(I), →⁴T_1g(F)(II), and →⁴T_1g(P)(III). Band energies in the two sets a and b, as obtained by absorption, A, and excitation, E, agree well: I: 17300(a, A), 17200(a, E), 16000(b, A), 16200(b, E); II: 24800(a, A), 24400(a, E); 22300(b, A), 22200(b, E); III: 28800(b,A) cm⁻¹. Evaluation of crystal field parameters from the bands in the electronic spectra yield Dq(a)=1730 cm⁻¹, Dq(b)=1600 cm⁻¹, B(a)=790 cm⁻¹, B(b)=620 cm⁻¹ (errors ca. ±10 cm⁻¹), again in agreement with values extracted from the λ³, λ⁴ excitation spectra. The CF-values of set a are close to those typical of Cr³⁺ substituting for Al in octahedra of other silicate minerals without constitutional OH⁻ as for sapphirine, mantle garnets or beryl, and are, therefore, interpreted as caused by Cr³⁺ substituting for Al in some or all of the M(1) to M(4) octaheda of the kyanite structure, which are crystallographically different but close in their mean Al–O distances, ranging from 1.896 to 1.919 A (Burnham 1963), and slight degrees of distortion. Hence, band set a originates from substitutive Cr³⁺ in the kyanite structural matrix. The CF-data of Cr³⁺ type b, expecially B, resemble those of Cr³⁺ in oxides, especially of corundum type solid solutions or eskolaite. This may be interpreted by the assumption that a fraction of the total chromium contents might be allocated in a precursor of a corundum type exsolution. Received: 3 January 1997 / Revised, accepted: 2 May 1997     

Single-crystal electronic absorption spectroscopy of synthetic chromium-, cobalt-, and vanadium-bearing pyropes at different temperatures and pressures

 Single crystals of synthetic vanadium-, chromium- and cobalt-bearing garnets, Pyr:V0.06, Pyr:V0.13, Pyr:Cr0.04, Pyr:Co0.10, and Gt:Co3.00, and a natural vanadium-bearing grossular, Gross:V0.07 (Cr³⁺ < 0.005), were studied by electronic absorption spectroscopy in the wavenumber range 35 000–5000 cm⁻¹ under ambient conditions and at temperatures up to 600 K and pressures up to 8 GPa. The T and P behavior of the absorption band energies and intensities shows the following for the different transition metal-bearing garnets: Cr: The thermal expansion of chromium octahedra are similar to and the Racah parameter the same in synthetic Cr-doped pyrope, α_poly≅ 1.3 × 10⁻⁵ K⁻¹, and in natural pyrope, α_poly≅ 1.5 × 10⁻⁵ K⁻¹, and B=655 cm⁻¹, respectively. Ca^2+[8]-free garnets have a slightly stronger crystal field at the Y^[6] site and, therefore, the energies of the two spin-allowed Cr³⁺ dd bands are ca. 300 cm⁻¹ higher in Mg-pyrope than in natural Ca-bearing pyrope. Co: Increasing temperature causes only a small thermal expansion of the cobalt dodecahedra. Increasing pressure gives rise to appreciable compression, which is similar to that of the Fe²⁺-dodecahedra in almandine, where k=125 ± 25 GPa. T and P dependence of the Co band intensities may be caused by strong spin-orbit coupling. V: Occurs in at least two valence states and structural sites: (1) V³⁺ in octahedral sites gives rise to two spin-allowed bands, at 17 220 cm⁻¹ and 24 600 cm⁻¹, whose temperature dependence is typical for spin-allowed dd transitions in centrosymmetric sites. (2) V⁴⁺, which causes a set of dd absorption bands similar to those observed in the spectrum of V⁴⁺-doped Zr[SiO₄]. The P behavior of the V absorption bands indicates an interaction between V³⁺ and V⁴⁺ species. Received: 27 June 2001 / Accepted: 19 December 2001     

Channel constituents in beryl

The electronic absorption spectra of Fe²⁺ in non-chromium beryls are examined. Fe²⁺ in the Al-rich six-coordinate site produces absorption bands at about 820 nm and 970 nm polarizedE‖c. Fe²⁺ in the channel produces bands at 820 nm (⊥c) and 2100 nm (‖c). Some blue beryls which are more intensely colored than most aquamarines, have an absorption band at ～700 nm (‖c) which is suggested to arise from an Fe²⁺/Fe³⁺ intervalence interaction. Fe²⁺ in both the six-coordinate site and the channel is identified in the Mössbauer spectra. The Mössbauer spectra of deep blue beryls are unusual and have not been satisfactorily explained. Color changes which accompany heating and irradiation are strongly influenced by the channel iron.     

OH in natural orthopyroxene: an in situ FTIR investigation at varying temperatures

In situ unpolarized and polarized Fourier transform infrared spectra of a natural orthopyroxene at varying temperatures were obtained using a heating stage attached on an Infrared microscope. The three main bands (3,595, 3,520 and 3,410 cm⁻¹) at room temperature are ascribed to OH fundamental stretching bands. With increasing temperature from room temperature to 500 °C, the 3,595 cm⁻¹ band shifts 20 cm⁻¹ to lower frequency. The total integral absorbance decreases with increasing temperature. These changes are reversible. Excluding the influences of dehydration, proton migration, thermal expansion, and changes in OH dipole direction, the change of integral absorbance with temperature reflects the temperature dependence of absorption coefficient due to the anharmonicity of OH vibration. Based on the integral absorption coefficient at room temperature (14.84 ppm⁻¹ cm⁻²) from Bell et al. (Am Mineral 80:463–474, 1995), the integral absorption coefficients at other temperatures are calculated. The variation of integral absorption coefficient between room temperature and 500 °C obtained in this study is about 18.5 % and may be greater at higher temperature according to the proposed linear relationship.     

High-temperature X-ray diffraction and Raman spectroscopy of diopside and pseudowollastonite

Diopside (CaMgSi₂O₆) and pseudowollastonite (CaSiO₃) have been studied by X-ray powder diffraction and Raman spectroscopy up to their respective melting points. In agreement with previous unit-cell parameters determinations below 1100 K, thermal expansion of diopside along the a and c axis is much smaller than along the b axis. For pseudowollastonite, the axis expansivity increases slightly in the order b>a>c. For both minerals, the change in unit-cell angles is very small and there are no anomalous variations of the other unit-cell parameters near the melting point. With increasing temperatures, the main changes observed in the Raman spectra are strong increases of the linewidths for those bands which mainly represent Si−O−Si bending (near 600 cm⁻¹) or involve Ca−O or Mg−O stretching, in the range 270–500 cm⁻¹ for diopside, and 240–450 cm⁻¹ for pseudowollastonite. At temperatures near the onset of calorimetric premelting effects, this extensive band widening results in a broad Raman feature that can no longer be deconvoluted into its individual components. No significant changes affect the Si−O streching modes. For both diopside and pseudowollastonite, premelting appears to be associated with enhanced dynamics of the alkaline-earth elements. This conclusion contrasts markedly with that drawn for sodium metasilicate in which weaker bonding of sodium allows the silicate framework to distort and deform in such a way as to prefigure the silicate entities present in the melt. Received 16 July 1997 / Revised, accepted: 6 March 1998     

Temperature-induced changes in the NIR spectra of hydrous albitic and rhyolitic glasses between 300 and 100 K

Near-infrared (NIR) absorption bands related to total water (4000 and 7050 cm⁻¹), OH groups (4500 cm⁻¹) and molecular H₂O (5200 cm⁻¹) were studied in two polymerised glasses, a synthetic albitic composition and a natural obsidian. The water contents of the glasses were determined using Karl Fischer titration. Molar absorption coefficients were calculated for each of the bands using albitic glasses containing between 0.54 and 9.16 wt.% H₂O and rhyolitic glasses containing between 0.97 and 9.20 wt.% H₂O. Different combinations of baseline type and intensity measure (peak height/area) for the combination bands at 4500 and 5200 cm⁻¹ were used to investigate the effect of evaluation procedure on calculated hydrous species concentrations. Total water contents calculated using each of the baseline/molar absorption coefficient combinations agree to within 5.8% relative for rhyolitic and 6.5% relative for albitic glasses (maximum absolute differences of 0.08 and 0.15 wt.% H₂O, respectively). In glasses with water contents >1 wt.%, calculated hydrous species concentrations vary by up to 17% relative for OH and 11% relative for H₂O (maximum absolute differences of 0.33 and 0.43 wt.% H₂O, respectively). This variation in calculated species concentrations is typically greater in rhyolitic glasses than albitic. In situ, micro-FTIR analysis at 300 and 100 K was used to investigate the effect of varying temperature on the NIR spectra of the glasses. The linear and integral molar absorption coefficients for each of the bands were recalculated from the 100 K spectra, and were found to vary systematically from the 300 K values. Linear molar absorption coefficients for the 4000 and 7050 cm⁻¹ bands decrease by 16–20% and integral molar absorption coefficients by up to 30%. Depending on glass composition and baseline type, the integral molar absorption coefficients for the absorption bands related to OH groups and molecular H₂O change by up to −5.8 and +7.4%, respectively, while linear molar absorption coefficients show less variation, with a maximum change of ∼4%. Using the new molar absorption coefficients for the combination bands to calculate species concentrations at 100 K, the maximum change in species concentration is 0.08 wt.% H₂O, compared with 0.39 wt.% which would be calculated if constant values were assumed for the combination band molar absorption coefficients. Almost all the changes in the spectra can therefore be interpreted in terms of changing molar absorption coefficient, rather than interconversion between hydrous species. Received: 17 December 1998 / Revised, accepted 8 July 1999     

A Raman spectroscopic investigation of Fe-rich sphalerite: effect of fe-substitution

A Raman spectroscopic study of Fe-rich sphalerite (Zn_{1 − x} Fe _x S) has been carried out for six samples with 0.10 ≤ x ≤ 0.24. Both the intensities and frequencies of the TO and LO modes of sphalerite are approximately independent of Fe concentration. However, the substitution of Zn by Fe results in five additional bands with frequencies between the TO (271 cm⁻¹) and LO (350 cm⁻¹) modes. Three of these bands are attributed to resonance modes (i.e. Y ₁, Y ₂ and Y ₃ modes). The fourth band (B mode) is assigned to a breathing mode of the nearest-neighbor sulfur atoms around the Fe atoms. The band at 337 cm⁻¹ is attributed to the presence of Fe³⁺. The excellent correlations between the normalized intensities of these five different modes and x _Fe show that these modes depend on Fe-content. Another extra mode at 287 cm⁻¹ is assigned to the presence of Cd in sphalerite.