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.     

The orientation and vibrational states of H2O in synthetic alkali-free beryl

 The polarized single-crystal Raman spectra of synthetic H₂O-containing alkali-free beryl were recorded at room and low temperatures, and the polarized single-crystal IR spectra at room temperature. The H₂O molecule in the channel cavities is characterized by a Raman-active symmetric stretching vibration (ν₁) at 3607 cm⁻¹ and an IR-active asymmetric stretch (ν₃) at 3700 cm⁻¹ at room temperature. At low temperatures this ν₃ mode is observed in the Raman. Weak ν₁ and ν₃ modes of a second type of H₂O are also observed in the Raman spectra but only at 5 K. The H⋯·H vector of the most abundant type of H₂O is parallel to the channel axis of beryl along [0 0 0 1]. The components of the polarizability tensor of the ν₁ mode of H₂O are similar to, but not exactly the same as, those of a free H₂O molecule. The Raman measurements indicate that the H₂O molecule is rotationally disordered around [0 0 0 1]. External translation and librational modes of H₂O could be observed as overtones with the internal H₂O-stretching modes. In the case of the librational motions, normal modes could also be observed directly in the Raman spectra at ∼200 cm⁻¹. The energies of the translational modes can be determined from an analysis of the overtones and are about 9 cm⁻¹ in energy (i.e., T_z). The energies of the librational modes are about 210 cm⁻¹ for R_x and 190 cm⁻¹ for R_y. Received: 8 April 1999 / Accepted: 5 April 2000     

天然与合成紫晶的红外和偏振拉曼光谱鉴定特征

天然紫晶与合成紫晶的鉴别是国内外珠宝鉴定实验室的一个难题,前人主要从双晶、色带、包裹体、红外吸收光谱特征等方面开展了研究。在利用红外光谱鉴别天然紫晶与合成紫晶时,不同的学者尚对3595cm-1或3543cm-1吸收峰作为诊断性还是指示性的判据存在不同认识。本文系统采集了典型的天然紫晶与合成紫晶样品,研究了利用红外光谱测试技术鉴别天然紫晶与合成紫晶的局限性,并尝试将偏振拉曼光谱应用于紫晶成因鉴别。结果表明:利用3595cm-1、3543cm-1红外吸收峰进行紫晶鉴别仅具有指示性意义,不能作为决定性的判定依据,偏振拉曼光谱可作为重要的补充。天然紫晶的偏振拉曼光谱(偏振方向:HH)均出现400cm-1的拉曼峰,而该峰在合成紫晶偏振拉曼光谱中缺失;合成紫晶的偏振拉曼光谱(偏振方向:HH)均具有795cm-1、448cm-1的拉曼峰,而这两个峰在天然紫晶偏振拉曼光谱中缺失。偏振拉曼光谱产生差异的原因可能与天然紫晶和合成紫晶内部晶格变形程度的不同有关。本文揭示的400cm-1、448cm-1和795cm-1偏振拉曼峰可作为鉴别紫晶成因的新依据。     

Low-temperature single-crystal Raman spectrum of pyrope

 The single-crystal polarized Raman spectra of synthetic pyrope, Mg₃Al₂Si₃O₁₂, were measured at room temperature and 5 K, as were the room-temperature unpolarized spectra of two natural pyrope-rich crystals. No major differences in the spectra between room temperature and 5 K are observed or are present between the synthetic and the natural crystals. The spectra are consistent with the proposal that the Mg cation is dynamically disordered and not statically distributed over subsites in the large triangular-dodecahedral E-site in pyrope. A low-energy band at about 135 cm⁻¹ softens and shows a large decrease in its line width with decreasing temperature. The presence of a weak, broad band at about 280 cm⁻¹ may be due to anharmonic effects, as could the one at 135 cm⁻¹. The latter is assigned to the rattling motion of Mg in pyrope in the plane of the longer Mg-O(4) bonds (Kolesov and Geiger 1998). The successful modeling of the anisotropic motion of the Mg cation in pyrope, which has an anharmonic character, provides a valuable test of the validity of empirical or semi-empirical lattice-dynamic calculations for silicates. Received: 10 May 1999 / Accepted: 10 April 2000     

Phase transitions in langbeinites II: Raman spectroscopic investigations of K2Cd2(SO4)3

Polarized single crystal Raman spectra of the langbeinite K₂Cd₂(SO₄)₃ were recorded for different polarisations. With a view to understanding the phase transition mechanism, the lattice vibrational spectra (0–300 cm^?1), as well as the SO₄ symmetric stretching mode v ₁ (1,022 cm^?1), were recorded at different temperatures. No soft modes were observed. From the study of the temperature variation of the integrated intensity I ₀ and band width Γ of the hard mode (1,022 cm^?1), both SO₄ libration and SO₄ order/disorder models were ruled out as possible phase transition models. On the other hand, the model of Speer and Salje (paper I), involving the distortion of the polyhedra around Cd and K ions, explains the observed temperature behaviour of the Raman spectra very well. The consequences of a possible hypothetical high-temperature phase are discussed.     

Surface modes in the infrared spectrum of hydrous minerals: the OH stretching modes of bayerite

The theoretical infrared (IR) and Raman spectra of bayerite (β-Al(OH)₃) are computed in the density functional theory framework, using the linear response theory. The results are consistent with the occurrence of six non-equivalent OH groups in a bayerite structure with space group P2₁/n. Similar to gibbsite, the transmission powder IR spectrum of bayerite in the region of the OH stretching bands is found to depend on the shape of particles. In particular, the broadening of the strong band observed at about 3,460 cm⁻¹ in the spectrum of Al hydroxides is related to the electrostatic charges occurring at the surface of the polarized dielectric particles. The experimental correlation observed between the shape of this band and morphological parameters has therefore a physical, instead of chemical, origin.     

Beryl-II,a high-pressure phase of beryl: Raman and luminescence spectroscopy to 16.4 GPa

The Raman and Cr³⁺ and V²⁺ luminescence spectra of beryl and emerald have been characterized up to 15.0 and 16.4 GPa, respectively. The Raman spectra show that an E _1g symmetry mode at 138 cm^?1 shifts negatively by ?4.57 (±0.55) cm^?1/GPa, and an extrapolation of the pressure dependence of this mode indicates that a soft-mode transition should occur near 12 GPa. Such a transition is in accord with prior theoretical results. Dramatic changes in Raman mode intensities and positions occur between 11.2 and 15.0 GPa. These changes are indicative of a phase transition that primarily involves tilting and mild distortion of the Si₆O₁₈ rings. New Raman modes are not observed in the high-pressure phase, which indicates that the local bonding environment is not altered dramatically across the transition (e.g., changes in coordination do not occur). Both sharp line and broadband luminescence are observed for both Cr³⁺ and V²⁺ in emerald under compression to 16.4 GPa. The R-lines of both Cr³⁺ and V²⁺ shift to lower energy (longer wavelength) under compression. Both R-lines of Cr³⁺ split at ~13.7 GPa, and the V²⁺ R₁ slope changes at this pressure and shifts more rapidly up to ~16.4 GPa. The Cr³⁺ R-line splitting and FWHM show more complex behavior, but also shift in behavior at ~13.7 GPa. These changes in the pressure dependency of the Cr³⁺ and V²⁺ R-lines and the changes in R-line splitting and FWHM at ~13.7 GPa further demonstrate that a phase transition occurs at this pressure, in good agreement with our Raman results. The high-pressure phase of beryl appears to have two Al sites that become more regular under compression. Hysteresis is not observed in our Raman or luminescence spectra on decompression, suggesting that this transition is second order in nature: The occurrence of a second-order transition near this pressure is also in accord with prior theoretical results. We speculate that the high-pressure phase (beryl-II) might be a mildly modulated structure, and/or that extensive twinning occurs across this transition.     

Temperature dependence of Raman spectra of the quartz- and rutile-types of GeO2

The temperature dependence (at ambient pressure) of the Raman spectra of both the quartz- and rutile-types of GeO₂ has been studied from 109 to 874?K. All spectra were corrected for the effects of temperature and are presented in their reduced form to allow a direct comparison of intensities at all temperatures. In the quartz-type GeO₂, the Raman bands above 400?cm^?1 exhibited relatively larger temperature dependences and at least four of the bands in this region vary nonlinearly with increasing temperature. Deconvolution of the most intense Raman band at 700?cm^?1 in the rutile-type GeO₂ revealed the presence of a previously unreported band at 684?cm^?1 at 298?K which may arise from splitting of the A_1g mode. A nonlinear temperature dependence was observed for all the Raman bands above 600?cm^?1 in the rutile-type GeO₂ with the new band at 684?cm^?1 exhibiting the largest curvature. In common with previous studies of rutile-type oxides, the B_1g mode at 171?cm^?1 showed anomalous behaviour by increasing linearly in frequency with increasing temperature. In a separate experiment, the oxidation of metallic germanium in air demonstrated that the quartz-type GeO₂ is the preferred form of germanium oxide at temperatures above 745?K at atmospheric pressure. Thermodynamic calculations predict that the rutile-form of GeO₂ should be the stable species under these conditions. This suggests that atmospheric gases may have a marked effect on the kinetics and stability of the quartz and rutile forms of GeO₂.     

Measurement of the polarized absorption spectra of synthetic transition metal-bearing silicate microcrystals in the spectral range 44,000-4,000 cm−1

A new single beam microtechnique has been developed for measuring the polarized absorption spectra in the region 44,000-4,000 cm^?1. Spectra of a natural garnet (Spess₇₀Alm₃₀), measured by the microtechnique and by conventional macrotechniques, are consistent and thus prove the applicability of the microtechnique described. It is possible to obtain well resolved spectra down to about 13,000 cm^?1 with crystals as small as about 10 μm. Thus spectra of crystals obtained in routine high-pressure high-temperature silicate syntheses can be measured. The polarized spectra of Mn³⁺, Fe³⁺, Fe²⁺, and Cr³⁺ in the following synthetic silicate minerals are presented: piemontite (I), acmite (II), orthoferrosilite (III), and kyanite (IV) or uvarovite (V), respectively. O-Cr³⁺, O-Mn³⁺, and O-Fe²⁺ charge transfer band maxima in the UV region are identified at 38,700 cm^?1, in V; at 33,200, 35,300, and 39,000 cm^?1, in I; and at 32,800, 35,200, and 37,300 cm^?1, in III, respectively. Bands in the region ≦25,000 cm^?1 are assigned to spin-allowed and spin-forbidden dd transitions as predicted from crystal field theoretical considerations for the foregoing ions in the respective structures.     

Quantum-mechanical calculation of the vibrational spectrum of beryl (Al4Be6Si12O36) at the Γ point

A quantum-mechanical calculation of the zone-centre phonon spectrum of beryl has been performed, by using an hybrid HF/DFT Hamiltonian (B3LYP). An excellent agreement with the experiment has been obtained, being the difference between the calculated and the experimental vibrational frequencies (Raman, IR-TO and IR-LO) less than 5 cm^?1 on average. In the few cases where a relatively large disagreement between calculated and experimental data is observed, an explanation can be found which attributes the reason of the discrepancies to the experimental data rather than to the calculated ones. The calculation (i) allows the identification, in the experimental spectra, of the peaks corresponding to fundamental modes, overtones, combination bands and leakage; (ii) solves problems of band assignements due to the presence of LO–TO splitting in the IR spectra; (iii) provides the frequencies of silent modes; (iv) permits a full analysis of the atomic motion corresponding to each normal mode.     

A note on the Raman spectra of water-bearing albite glasses

The Raman spectra of albite glasses with 4.5 and 6.6 weight percent water have been obtained, and are compared with that of a dry sample. The hydrous glasses show bands near 3600 cm^?1 due to O-H stretching, and a previously unreported weak band near 1600 cm^?1 due to bending of molecular H₂O. Other weak spectral features are discussed, and the effect of dissolved water on the aluminosilicate framework vibrations is considered.     

Application of infrared spectroscopy to studies of silicate glass structure: Examples from the melilite glasses and the systems Na2O-SiO2 and Na2O-Al2O3-SiO2

Infrared (IR) and Raman spectroscopic methods are important complementary techniques in structural studies of aluminosilicate glasses. Both techniques are sensitive to small-scale (<15 Å) structural features that amount to units of several SiO₄ tetrahedra. Application of IR spectroscopy has, however, been limited by the more complex nature of the IR spectrum compared with the Raman spectrum, particularly at higher frequencies (1200–800 cm^?1) where strong antisymmetric Si-O and Si-O-Si absorptions predominate in the former. At lower frequencies, IR spectra contain bands that have substantial contributions from ‘cage-like’ motions of cations in their oxygen co-ordination polyhedra. In aluminosilicates these bands can provide information on the structural environment of Al that is not obtainable directly from Raman studies. A middle frequency envelope centred near 700 cm^?1 is indicative of network-substituted AlO₄ polyhedra in glasses with Al/(Al+Si)>0·25 and a band at 520–620cm^?1 is shown to be associated with AlO₆ polyhedra in both crystals and glasses. The IR spectra of melilite and melilite-analogue glasses and crystals show various degrees of band localization that correlate with the extent of Al, Si tetrahedral site ordering. An important conclusion is that differences in Al, Si ordering may lead to very different vibrational spectra in crystals and glasses of otherwise gross chemical similarity.     

Coordination of water molecules with Na+ cations in a beryl channel as determined by polarized IR spectroscopy

Subtle variations of frequencies in the infrared (IR) absorption spectra of beryl have been predicted based on the coordination between extra-framework cations and water molecules in two orientations (referred to as type I and type II) trapped within the channel. In this study, the polarized IR spectra of hydrated synthetic beryl and natural beryl were measured to clarify the relationships between the frequencies of the absorption bands and the coordination states of type II water. Na⁺ was assumed to be the predominant cation coordinated to type II water in our samples, as determined by chemical analyses. These measurements revealed a clear quantitative linear relationship in absorbance between bands at 3,602 and 1,619 and at 3,589 and 1,631 cm⁻¹. On the basis of experimental and theoretical studies, we assigned these pairs of bands to the ν₁ and ν₂ modes of doubly coordinated type II H₂O and to singly coordinated type II H₂O, respectively. These assignments were supported by IR measurements of annealed natural beryl. We also conducted dehydration studies of natural beryl, in which two observed dehydration peaks, at 600 and 750°C, suggested the dehydration of type I and type II water, respectively.     

Vibrational interactions of tetrahedra in silicate glasses and crystals

Normal coordinate calculations have been carried out on partially polymerized simple silicate crystals, including Li and Na di- and metasilicates, Li and Gd pyrosilicates, thortveitite and rankinite. In the antisymmetric Si-O stretching modes which are active at 800–1200 cm^?1 in infrared spectra, Si-Obr vibrations occur at higher frequencies than Si-Onb vibrations if the bonds have equivalent strengths. However, this relationship is usually reversed when bridging oxygens are overbonded and non-bridging oxygens are underbonded in terms of Pauling bond strengths, a situation which is generally more common in crystals. An observed bimodality of the high-frequency envelope in infrared spectra of glasses in the alkali oxide-silica systems may be somewhat fortuitous, with the high frequency component (ca. 1100 cm^?1) representing underbonded non-bridging oxygens and saturated bridging oxygens, and the lower-frequency component (ca. 1000 cm^?1) mainly oversaturated bridging oxygens. Significant differences between crystals and glasses in the number and location of the main high-frequency infrared peaks suggest that there are short-range bonding rearrangements in the glasses, and that crystallite models are not applicable. Mid-frequency (600–800 cm^?1) infrared modes in silicates more polymerized than the pyrosilicate (Si₂O₇) appear to be mostly antisymmetric modes in which Si rattles against bridging oxygens, rather than symmetric stretching modes.     

Spectroscopic and bond-topological investigation of interstitial volatiles in beryl from Slovakia

Nine beryl samples from Western Carpathians, Slovakia, were investigated by infrared and Raman spectroscopy and differential thermal analysis. Two types of water H₂O I and H₂O II were detected. Infrared spectroscopy proved the presence of water type I and II in the presence of alkali cations with several bands: (1) symmetric stretching vibration—ν₁; (2) antisymmetric stretching mode—ν₃; (3) bending vibration—ν₂. The presence of singly and doubly coordinated type II water (IIs and IId) was confirmed by single-crystal IR spectroscopy. From Raman spectra a band at 3606 cm^?1 was assigned to ν₁ of water type I and the range of 3597–3600 cm^?1 to water type II. The presence of doubly coordinating water indicates a relatively highly hydrated environment with the presence of alkali ions including Na as the dominant cation coordinated by H₂O II. CO₂ bands were detected only by single-crystal IR spectroscopy. Thermal analysis proved total water loss in the range of 1.4–2.0 wt% and three main dehydration events. Based on the study of bond-topological arrangements two molecules of H₂O IId are each bound with two H···O1 bonds and one Na–O_W bond with an angular distortion, and by releasing one H₂O molecule more stable H₂O IIs is produced. The H₂O I molecule is bound only by two equivalent hydrogen bonds. The H₂O IIs molecule with a Na–O_W bond strength of 0.28 vu and two H···O1 bonds of 0.14 vu without any forced angular distortion is the most stable of all.     

Vibrational spectroscopy of beryllium aluminosilicates: Heat capacity calculations from band assignments

Far-infrared, mid-IR, and Raman powder spectra were measured on six phases (bromellite, chrysoberyl, phenakite, bertrandite, beryl, and euclase) in the system BeO-Al₂O₃-SiO₂-H₂O. A single-crystal absorption spectrum of IR fundamentals in beryl is also presented, which more closely resembles the powder absorption spectrum than it does absorption spectra calculated from single-crystal reflection data. Assignments of the SiO₄ and BeO₄ internal vibrations are made in accordance with each mineral's symmetry and composition and by comparison to structural analogs. Heat capacities C _v calculated for these partial band assignments agree with C _v derived from experimental C _p for all six phases, provided that Kieffer's (1979c) model is slightly modified to correctly enumerate both Si-O and Be-O stretching modes in the high frequency region (>750 cm^?1). Si-O stretching bands were found to out-number Be-O stretching modes in the high-energy region of the vibrational spectra with two exceptions: (1) For those phases containing oxygen ions not coordinated to silicon, vibrations occurring at v>1,080 cm^?1 that are attributable to Be-O (H) stretching must be treated separately in the model in order to calculate C _v accurately. (2) Minerals consisting entirely of interlocking Si and Be tetrahedra (i.e., phases without Al or OH) can be modeled by one optic continuum representing all optical modes. These results, along with the occurrence of very low energy lattice vibrations for Be-silicates within Al, suggests that although Be-O bonds are generally weaker than neighboring Si-O bonds, Be mimics the network-forming characteristic of Si to a limited extent.     

A hitherto unrecognised band in the Raman spectra of silica rocks: influence of hydroxylated Si–O bonds (silanole) on the Raman moganite band in chalcedony and flint (SiO<Subscript>2</Subscript>)

Chalcedony is a spatial arrangement of hydroxylated nanometre-sized α-quartz (SiO₂) crystallites that are often found in association with the silica mineral moganite (SiO₂). A supplementary Raman band at 501 cm⁻¹ in the chalcedony spectrum, attributed to moganite, has been used for the evaluation of the quartz/moganite ratio in silica rocks. Its frequency lies at 503 cm⁻¹ in sedimentary chalcedony, representing a 2 cm⁻¹ difference with its position in pure moganite. We present a study of the 503 cm⁻¹ band’s behaviour upon heat treatment, showing its gradual disappearance upon heating to temperatures above 300 °C. Infrared spectroscopic measurements of the silanole (SiOH) content in the samples as a function of annealing temperature show a good correlation between the disappearance of the 503 cm⁻¹ Raman band and the decrease of structural hydroxyl. Thermogravimetric analyses reveal a significant weight loss that can be correlated with the decreasing of this Raman band. X-ray powder diffraction data suggest the moganite content in the samples to remain stable. We propose therefore the existence of a hitherto unknown Raman band at 503 cm⁻¹ in chalcedony, assigned to ‘free’ Si–O vibrations of non-bridging Si–OH that oscillate with a higher natural frequency than bridging Si–O–Si (at 464 cm⁻¹). A similar phenomenon was recently observed in the infrared spectra of chalcedony. The position of this Si–OH-related band is nearly the same as the Raman moganite band and the two bands may interfere. The actually observed Raman band in silica rocks might therefore be a convolution of a silanole and a moganite vibration. These findings have broad implications for future Raman spectroscopic studies of moganite, for the assessment of the quartz/moganite ratio, using this band, must take into account the contribution from silanole that are present in chalcedony and moganite.     

Experimental and theoretical study of the vibrational properties of diaspore (α-AlOOH)

Vibrational properties of diaspore, α-AlOOH, have been re-investigated using room-temperature single-crystal Raman spectroscopy and low-temperature powder infrared (IR) transmission spectroscopy. First-principles harmonic calculations based on density functional theory provide a convincing assignment of the major Raman peaks and infrared absorption bands. The large width of the Raman band related to OH stretching modes is ascribed to mode–mode anharmonic coupling due to medium-strength H-bonding. Additional broadening in the powder IR spectrum arises from depolarization effects in powder particles. The temperature dependence of the IR spectrum provides a further insight into the anharmonic properties of diaspore. Based on their frequency and temperature behavior, narrow absorption features at ~2,000 cm⁻¹ and anti-resonance at ~2,966 cm⁻¹ in the IR spectrum are interpreted as overtones of fundamental bending bands.     

Raman spectra of polycrystalline microdiamond inclusions in zircons,and ultrahigh-pressure metamorphism of a quartzofeldspathic rock from the Erzgebirge terrane,Germany

ABSTRACT

Polycrystalline microdiamonds are rare in ultrahigh-pressure (UHP) rocks worldwide. Among samples collected at Erzgebirge, Germany, we found abundant polycrystalline microdiamonds as inclusions in zircons from a quartzofeldspathic rock. To illuminate their origin and forming age, we investigated morphologies and Raman spectra of 52 microdiamond inclusions, and dated the zircon host. The zircons have low Th/U values (0.03–0.07) and a concordia U/Pb age of 335.8 ± 1.9 Ma. Polycrystalline diamond (10–40 µm) consists of many fine-grained crystals (1.5–3 µm) with different orientations; discrete single diamonds (2–20 µm) are rare. All measured Raman spectra show an intense diamond band at 1332–1328 cm^?1 and have a negative correlation with full width at half maximum (FWHM) of 5.8–11.3 cm^?1. These data combined with previously reported diamond band data (1331–1337 cm^?1) are compatible with those of diamond inclusions in various host minerals from other UHP terranes, but are different from those of ureilite diamonds. The Erzgebirge microdiamonds in zircon do not display visible disordered sp³-carbon, but show downshifting of the Raman band from the ideal value (1332 cm^?1), and have a broader diamond band (FWHM >3 cm^?1) than those of well-ordered diamonds. These features may reflect imperfect ordering due to rapid nucleation/crystallization during UHP metamorphism and rapid exhumation of the UHP terrane. Graphite inclusions in zircon show a typical G-band at 1587 cm^?1. Our study together with previously reported C-isotopic compositions (δ¹³C, ?17 to ?27‰) of diamond and occurrences of fluid/melt inclusions in diamond and garnet indicates that Erzgebirge microdiamonds are metamorphic, have an organic carbon source, and crystallized from aqueous fluids. Limited long-range ordering suggested by the Raman spectra is a function of the P–T time of crystallization and subsequent thermal annealing on decompression. Combined with regional geology, our work further constrains the tectonic evolution of the Erzgebirge terrane.     

Single crystal absorption spectra of synthetic Ti,Fe-substituted pyropes

Synthetic pyrope crystals up to 0.5 mm in diameter, substituted by titanium or by titanium plus iron, were grown under defined conditions of P, T, $f_{O_2 }$ in the presence of water using a piston-cylinder device. The crystals were characterized by X-ray and microprobe techniques. Their single-crystal optical absorption spectra were measured by means of a microscope-spectrometer. Two absorption bands at 16100 and 22300 cm{cm-1} in the spectra of pale-blue Fe-free Ti-bearing pyropes, grown under reduced conditions, were identified as originating from spin-allowed transitions, derived from ² T _2g → ² E _g of octahedral Ti³⁺ ions. The splitting value of the excited ²E _g state, 6200 cm^-1, and the crystal field parameter of Ti³⁺ in pyrope Δ ₀ = 19 200 cm^-1 are both in agreement with literature data. In spectra of brown Fe, Ti-bearing garnets, a broad band at 23000 cm^-1 was interpreted as a Fe^2+[8] → Ti^4+[6] charge-transfer band. The spectral position and width of this band agree with those observed for a FeTi charge transfer band in natural garnets. Fe, Ti-containing garnets synthesized at relatively high oxygen fugacity (10^-11,0 atm), which permits a fraction of Fe³⁺ to enter the garnet, show an additional Fe^2+[8] → Fe^3+[6] charge transfer band at 19800 cm^-1.