Single crystal raman studies of pyrite-type RuS2, RuSe2, OsS2, OsSe2, PtP2, and PtAs2

Single crystal Raman spectra of pyrite-type RuS₂, RuSe₂, OsS₂, OsSe₂, PtP₂, and PtAs₂ are presented and discussed with reference to the energies of the X-X stretching modes _x-x (A _g, F _g) and the X₂ librations (E, 2F_g). The main results obtained are (i) strong Raman resonance effects, (ii) different sequences for _x-x (A _g) and (E _g), i.e., R_{x_2 } $$ " align="middle" border="0"> for PtP₂ and PtAs₂ and R_{x_2 } $$ " align="middle" border="0"> for OsS₂, owing to the interplay of intraionic and interionic lattice forces, (iii) greater strengths for the intraionic P-P and As-As bonds compared to the S-S and Se-Se bonds, respectively, and (iv) a strong influe_gnce of the metal ions on the strength of the X-X bonds.This is contribution LXI of a series of papers on lattice vibration spectra     

Infrared reflection spectra,directional dispersion of the phonon modes and dynamical effective charges of FeS2-Marcasite

The polarized far-infrared reflection spectra of single crystals of FeS₂-marcasite are presented in the range from 40–700 cm^?1. The spectra show 7 reststrahlen bands, as predicted by group theory. The oscillator parameters ?_{α ∞}, ω_{α f}, ?_{α f}, γ_{α f}, and the transversal and longitudinal optical phonon frequencies ω_TO and ω_LO as well as effective ionic charges and oscillator strength weighted mean phonon frequencies were calculated. The anisotropic behaviour of these quantities is discussed in relation to the data for FeS₂-pyrite. It is shown that the ionicity of marcasite is considerably smaller than that of pyrite, especially in the a and c direction. The directional dependence of the phonon frequencies is given and discussed with regard to the spectra of polycrystalline samples.     

X-ray absorption near-edge spectra of transition metal disulfides FeS2 (pyrite and marcasite), CoS2, NiS2 and CuS2, and their isomorphs FeAsS and CoAsS

Metal K- and L₃-, sulfur K- and arsenic K- and L₃-edge X-ray absorption near-edge spectra of a series of metal disulfides, FeS₂ (both pyrite and marcasite), CoS₂, NiS₂, and CuS₂, and their isomorphs, FeAsS and CoAsS, are presented. The features in this region of these spectra are interpreted using band structure and molecular orbital calculations in terms of the transitions from the 1s or 2p_3/2 state to unoccupied states. The 3d transition metal L₃-edge spectra of these materials show dependence on the degree of multiplet splitting in the final state, and thus offer less information on the electronic ground state. There are substantial differences in the spectra of the isostructural materials, whereas the spectra of the isotopes pyrite and marcasite show several similarities, illustrating the dependence of near-edge region on electronic structure.     

Characterization of the structure and the surface reactivity of a marcasite thin film

A thin film of marcasite, FeS₂, was synthesized under vacuum and its structure and reactivity under oxidizing conditions was investigated by means of diffraction and surface analytical techniques, respectively. Synthesis of the film was carried out by codepositing Fe and S₂ onto a Ta support. The thickness of the film could be varied from approximately 10 Å to 1 μm. High-resolution S 2p synchrotron-based photoemission showed S22−, with undetectable amounts of S²⁻ impurity that is typically present on natural sample surfaces. X-ray diffraction of the micron-thick films showed that the film crystallized in the marcasite phase of FeS₂. Atomic force microscopy indicated that the thin film had a nanometer-scale roughness suggesting the film contained defects such as steps and kinks. X-ray photoelectron spectroscopy studies found the thin marcasite film to be more reactive than natural pyrite (the most ubiquitous FeS₂ dimorph) after exposure to a gaseous O₂/H₂O environment on the basis of the amount of sulfate formation. Likely the oxidation of marcasite was dominated by its short-range order (e.g., presence of steps), because the density of nonstoichiometric defect sites (e.g., S²⁻) was low as assessed by photoelectron spectroscopy.     

Atomistic simulation of the structure and elastic properties of pyrite (FeS2) as a function of pressure

Interatomic potential parameters have been derived at simulated temperatures of 0 K and 300 K to model pyrite FeS₂. The predicted pyrite structures are within 1% of those determined experimentally, while the calculated bulk modulus is within 7%. The model is also able to simulate the properties of marcasite, even though no data for this phase were included in the fitting procedure. There is almost no difference in results obtained for pyrite using the two potential sets; however, when used to model FeS₂ marcasite, the potential fitted at 0 K performs better. The potentials have also been used to study the high-pressure behaviour of pyrite up to 44 GPa. The calculated equation of state gives good agreement with experiment and shows that the Fe–S bonds shorten more rapidly that the S–S dimer bonds. The behaviour of marcasite at high pressure is found to be similar to that of pyrite.     

First-principles calculations of the thermodynamic mixing properties of arsenic incorporation into pyrite and marcasite

The thermodynamic mixing properties of As into pyrite and marcasite have been investigated using first-principles and Monte Carlo calculations in order to understand the incorporation of this important metalloid into solid solution. Using quantum-mechanical methods to account for spin and electron transfer processes typical of sulfide minerals, the total energies of different As–S configurations were calculated at the atomic scale, and the resulting As–S interactions were incorporated into Monte Carlo simulations. Enthalpies, configurational entropies and Gibbs free energies of mixing show that two-phase mixtures of FeS₂ (pyrite or marcasite) and FeAsS (arsenopyrite) are energetically more favorable than the solid solution Fe(S,As)₂ (arsenian pyrite or marcasite) for a wide range of geologically relevant temperatures. Although miscibility gaps dominate both solid solution series, the solubility of As is favored for X_As < 0.05 in iron disulfides. Consequently, pyrite and marcasite can host up to ∼6 wt.% of As in solid solution before unmixing into (pyrite or marcasite) + arsenopyrite. This finding is in agreement with previously published HRTEM observations of As-rich pyrites (> 6 wt.% As) that document the presence of randomly distributed domains of pyrite + arsenopyrite at the nanoscale. According to the calculations, stable and metastable varieties of arsenian pyrite and marcasite are predicted to occur at low (X_As < 0.05) and high (X_As > 0.05) As bulk compositions, respectively.     

Pyrite,marcasite, and arsenopyrite type minerals: Crystal chemical and structural principles

Quantitative molecular orbital (MO) calculations and qualitative perturbational MO arguments are used to interpret the spectra and structure of transition metal dichalcogenides and related compounds. Competition between pyrite (FeS₂), marcasite (FeS₂) and loellingite (FeAs₂) structure types is explained in terms of the number of electrons occupying a set of MO's obtained from the mixing of dianion (A ₂) orbitals and metal (M) dσ orbitals. Direct metal-metal d orbital interaction is argued to be small. Attention is focused upon the M - A - M angles which differ substantially among the three structure types as a consequence of varying numbers of electrons in orbitals which closely resemble the pπ* orbitals of the dianions. Variations in M - A and A - A distances can also be understood in terms of the occupations of this set of MO's. Disulfide valence region photo-emission spectra are interpreted in terms of calculations on MS₆ and S₆ molecular clusters. M3d orbitals are found to progressively approach the S3p orbitals with increasing atomic number of M from Fe to Ni. For CuS₂ comparison of calculation and experiment supports an approximate electron configuration of Cu⁺¹ S ₂ ^?1 .     

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.     

Lattice dynamics of pyrite FeS2 — polarizable-ion model

Lattice dynamical calculations of the pyrite FeS₂ were performed using the polarizable-ion model (PIM) with different sets of short-range force constants. Not until the mean deviations between the observed and the calculated phonon energies become smaller than 3 cm^-1, the true force field can be established. In the case of only slightly greater deviations, the force fields computed differ strongly being without any physical meaning. The results are discussed with respect to the force constants K _i , F _i , and H _i , the effective dynamic charges and polarizabilities of the atoms involved, and the eigenvectors and potential energy distributions of the phonon modes. The most important short-range force constants are K ₁ (Fe-S stretching): 0.5 N cm^-1, K ₂ (internal stretching of the S₂ units): 1.0 N cm^-1, F ₁ (Fe^....Fe stretching): 0.2 N cm^-1, which indicate repulsive interactions of Fe atoms due to the occupied t _2g orbitals despite the relatively large Fe?Fe distances of 383 pm, and F ₂ and F ₃ (both intermolecular S₂?S₂ interactions): 0.2 N cm^-1. The great TO/LO splittings of some of the IR allowed phonon modes (species F _u) are caused by the large polarizabilities (2.4^.10⁶ and 3.3^.10⁶ pm³) of the atoms involved rather than by their effective charges (Fe: 0.2 e).     

First-principles study of high-pressure stability,structure, and elasticity of FeS2 polymorphs

The pressure-dependent elastic properties of the Fe–S system are important to understand the dynamic properties of the Earth’s interior. We have therefore undertaken a first-principles study of the structural and elastic properties of FeS₂ polymorphs under high pressure using a method based on plane-wave pseudopotential density function theory. The lattice constants, elastic constants, zero-pressure bulk modulus, and its pressure derivative of pyrite are in good agreement with the previous experiments and theoretical approaches; the lattice constants of marcasite are also consistent with the available experimental data. Calculations of the elastic constants of pyrite and marcasite have been determined from 0 to 200 GPa. Based on the relationship between the calculated elastic constants and the pressure, which can provide the stability of mineral, it would appear that pyrite is stable, whereas marcasite is unstable when the pressure rises above 130 GPa. Static lattice energy calculations predict the marcasite-to-pyrite phase transition to occur at 5.4 GPa at 0 K.     

The 57Fe Mössbauer parameters of pyrite and marcasite with different provenances

Eighteen pyrite and twelve marcasite samples which have different provenances have been investigated to determine the systematics of the influence of mineralogical and geological factors on the ⁵⁷Fe Mössbauer spectra at 298 K. The following results have been obtained: there is no ambiguity in distinguishing single phase pyrite from single phase marcasite by means of ⁵⁷Fe Mössbauer spectroscopy at 298 K. At 298 K the average electric quadrupole splitting, 〈ΔE_Q〉, and average isomer shift, 〈δ〉, with respect to Fe metal, are 0.6110 ± 0.0030 mm s^?1 and 0.313 ± 0.008 mm s^?1, respectively, for the 18 pyrites; 〈ΔE_Q〉 = 0.5030 ± 0.0070 mm s^?1 and 〈δ〉 = 0.2770 ± 0.0020 mm s^?1 for the 12 marcasites. At 77 K, ΔE_Q is 0.624 mm s^?1 for pyrite and 0.508 mm s^?1 for marcasite. In distinguishing pyrites from marcasites, spectra obtained at 77 K are not warranted.The Mössbauer parameters of pyrite and marcasite exhibit appreciable variations, which bear no simple relationship to the geological environment in which they occur but appear to be selectively influenced by impurities, especially arsenic, in the pyrite lattice. Quantitative and qualitative determinations of pyrite/marcasite mechanical mixtures are straightforward at 298 K and 77 K but do require least-squares computer fittings and are limited to accuracies ranging from ±5 to ±15 per cent by uncertainties in the parameter values of the pure phases. The methodology and results of this investigation are directly applicable to coals for which the presence and relative amounts of pyrite and marcasite could be of considerable genetic significance.     

Structural and vibrational behaviour of fluorapatite with pressure. Part II: in situ micro-Raman spectroscopic investigation

 High-pressure Raman investigations were carried out on a synthetic fluorapatite up to about 7 GPa to analyse the behaviour of the phosphate group's internal modes and of its lattice modes. The Raman frequencies of all modes increased with pressure and a trend toward reduced splitting was observed for the PO₄-stretching modes [(ν_3a(A_g) and ν_3b(A_g); ν_3a(E_2g) and ν_3b(E_2g)] and the PO₄ out-of-plane bending modes [ν_4a(A_g) and ν_4b(A_g)]. The pressure coefficients of phosphate modes ranged from 0.0047 to 0.0052 GPa⁻¹ for ν₃, from 0.0025 to 0.0044 GPa⁻¹ for ν₄, from 0.0056 to 0.0086 GPa⁻¹ for ν₂ and 0.0046 for ν₁ GPa⁻¹, while the pressure coefficients of lattice modes ranged from 0.0106 to 0.0278 GPa⁻¹. The corresponding Grüneisen parameters varied from 0.437 to 0.474, 0.428, 0.232 to 0.409 and 0.521 to 0.800 for phosphate modes ν₃, ν₁, ν₄, ν₂, respectively, and from 0.99 to 2.59 for lattice modes. The vibrational behaviour was interpreted in view of the high-pressure structural refinement performed on the same crystal under the same experimental conditions. The reduced splitting may thus be linked to the reduced distortion of the environment around the phosphate tetrahedron rather than to the decrease of the tetrahedral distortion itself. Moreover, the amount of calcium polyhedral compression, which is about three times the compression of phosphate tetrahedra, may explain the different Grüneisen parameters. Received: 25 April 2000 / Accepted: 20 December 2000     

Aqueous Cr(VI) reduction by pyrite: Speciation and characterisation of the solid phases by X-ray photoelectron, Raman and X-ray absorption spectroscopies

Optical microscopy, confocal Raman micro-spectrometry, X-ray photoelectron micro-spectroscopy (XPS) and synchrotron based micro-X-ray fluorescence (XRF), micro-X-ray absorption near edge spectroscopy (XANES) and micro-extended X-ray absorption fine structure (EXAFS) were used to investigate the reduction of aqueous Cr(VI) by pyrite. Special emphasis was placed on the characterisation of the solid phase formed during the reaction process. Cr(III) and Fe(III) species were identified by XPS analyses in addition to non-oxidised pyrite. Optical microscopy images and the corresponding Raman spectra reveal a strong heterogeneity of the samples with three different types of zones. (i) Reflective areas with E_g and A_g Raman wavenumbers relative to non-oxidised pyrite are the most frequently observed. (ii) Orange areas that display a drift of the E_g and A_g pyrite vibration modes of −3 and −6 cm⁻¹, respectively. Such areas are only observed in the presence of Cr(VI) but are not specifically due to this oxidant. (iii) Bluish areas with vibration modes relative to a corundum-like structure that can be assigned to a solid solution Fe_2−xCr_xO₃, x varying between 0.2 and 1.5. The heterogeneity in the spatial distribution of chromium observed by optical microscopy and associated Raman microspectroscopy is confirmed by μ-XRF. In agreement with both solution and XPS analyses, these spectroscopies clearly confirm that chromium is in the trivalent state. XANES spectra in the iron K-edge pre-edge region obtained in rich chromium areas reveal the presence of ferric ion thus revealing a systematic association between Cr(III) and Fe(III). In agreement with Raman analyses, Cr K-edge EXAFS can be interpreted as corresponding to Cr atoms involved in a substituted-type hematite structure Fe_2−xCr_xO₃.     

Vibrational spectra of single-crystal topaz

A single-crystal of topaz was studied by Raman spectroscopy to assign the internal modes of the high-frequency range and to compare with infrared data. All active modes exhibit an important Davydov splitting (150 cm^?1) but we have found a small Bethe splitting (14.5 cm^?1) consistent with a very regular SiO₄ tetrahedron. Because of a high value of v ₁ (～920 cm^?1) the Raman active modes present a mixed v ₁/v ₃ character. Finally the substitution of OH for F splits an A _g internal mode and lead to some proper modes at 3650 cm^?1, 3639 cm^?1 and 1165 cm^?1.     

Computer simulation in hydrothermal systems with allowance for nonideality of sphalerite and pyrrhotite

To enhance the computer simulation of hydrothermal processes using the HCh program package, an external ZnS_FeS module has been created on the basis of a nonideal asymmetric model of sphalerite solid solution. FeS and ZnS activity coefficients computed in line with this model within a temperature range 200?C350°C lead to the decrease in FeS mole fraction (X _FeS) in sphalerite by 3.0?C1.5 times as compared with the ideal model. The calculated data on composition of sphalerite at the pyrite-pyrrhotite buffer with allowance for pyrrhotite nonideality are consistent with experimental results within the limits of 2% X _FeS of its value (0.215). A nonlinear relationship logX _FeS versus $\left( {\log f_{S_2 } } \right)$ . has been established, involving additional calculated data on equilibria of sphalerite with pyrite and magnetite, as well as pyrite and barite. With transition from pyrrhotite to magnetite and barite, a FeS mole fraction in sphalerite decreases to 0.1 and 0.006, respectively, because of increase in sulfur fugacity. The feasibility of using the calculation results based on the nonideal model of sphalerite for interpretation of natural data is exemplified in the Rainbow ore occurrence at the Mid-Atlantic Ridge (MAR). The computed pyrite-pyrrhotite and pyrite-cubanite-chalcopyrite buffer equilibria (X _FeS = 0.215 and 0.10?C0.12, respectively) are consistent with compositions of sphalerite in the pyrrhotite-cubanite-sphalerite and sphalerite ores (X _FeS = 0.20?C0.33 and 0.05?C0.14, respectively).     

Polarized electronic absorption spectra of 3d3-configurated tetravalent manganese in octahedral fields of Mn(SeO3)2

Polarized optical absorption spectra of Mn(IV) in octahedral crystal fields of Mn(SeO₃)₂ have been studied by means of microscope-spectrometry in the range 40000-4000 cm^?1 and at temperatures between 113 K and 293 K. Intense charge-transfer absorptions (linear absorption coefficient α ? 30000 cm^?1) completely mask the d-d transitions in the UV and VIS region above ≈23000 cm^?1. The optical electronegativity χ _opt of Mn(IV) in Mn(SeO₃)₂ is estimated to be 2.7. In accordance with the d ₃ configuration of tetravalent manganese three d-d bands observed at ambient temperatures at 13250, 14137 (α≈50 cm^?1) and ≈18500 cm^?1 (α≈500–800 cm^?1) are assigned to the spin forbidden ⁴ A _2g →² E _g and ⁴ A _2g →² T _1g transitions as well as to the first spin allowed ⁴ A _2g →⁴ T ^2g transition, respectively. These assignments allow the calculation of the following ligand field parameters: Dq ≈ 1850 cm^?1, B ₅₅ = 869 cm^?1 (β ₅₅ = 0.82), and C = 2346 cm^?1 (293 K).     

Rates of reaction of pyrite and marcasite with ferric iron at pH 2

The relative reactivities of pulverized samples (100–200 mesh) of 3 marcasite and 7 pyrite specimens from various sources were determined at 25°C and pH 2.0 in ferric chloride solutions with initial ferric iron concentrations of 10^?3 molal. The rate of the reaction:

$\text{FeS}{}_2\text{+ 14}\text{Fe}{}^{\mathrm{3+}}\text{+ 8}\text{H}{}_2\text{O}\text{= 15}\text{Fe}{}^{\mathrm{2+}}\text{+ 2}\text{SO}{}^{\mathrm{2?}}{}_4\text{+ 16}\text{H}{}^{\mathrm{+}}$

was determined by calculating the rate of reduction of aqueous ferric ion from measured oxidation-reduction potentials. The reaction follows the rate law:

where m_Fe³⁺ is the molal concentration of uncomplexed ferric iron, k is the rate constant and $\text{A}\text{M}$ is the surface area of reacting solid to mass of solution ratio. The measured rate constants, k, range from 1.0 × 10^?4 to 2.7 × 10^?4 sec^?1 ± 5%, with lower-temperature/early diagenetic pyrite having the smallest rate constants, marcasite intermediate, and pyrite of higher-temperature hydrothermal and metamorphic origin having the greatest rate constants. Geologically, these small relative differences between the rate constants are not significant, so the fundamental reactivities of marcasite and pyrite are not appreciably different.The activation energy of the reaction for a hydrothermal pyrite in the temperature interval of 25 to 50°C is 92 kJ mol^?1. This relatively high activation energy indicates that a surface reaction controls the rate over this temperature range. The BET-measured specific surface area for lower-temperature/early diagenetic pyrite is an order of magnitude greater than that for pyrite of higher-temperature origin. Consequently, since the lower-temperature types have a much greater $\text{A}\text{M}$ ratio, they appear to be more reactive per unit mass than the higher temperature types.     

Single-crystal EPR and DFT study of a <Superscript>VI</Superscript>Al–O<Superscript>−</Superscript>–<Superscript>VI</Superscript>Al center in jeremejevite: electronic structure and <Superscript>27</Superscript>Al hyperfine constants

Single-crystal electron paramagnetic resonance (EPR) spectra of a gem-quality jeremejevite, Al₆B₅O₁₅(F, OH)₃, from Cape Cross, Namibia, reveal an S = 1/2 hole center characterized by an ²⁷Al hyperfine structure arising from interaction with two equivalent Al nuclei. Spin-Hamiltonian parameters obtained from single-crystal EPR spectra at 295 K are as follows: g ₁ = 2.02899(1), g ₂ = 2.02011(2), g ₃ = 2.00595(1); A ₁/g _e β _e  = −0.881(1) mT, A ₂/g _e β _e  = −0.951(1) mT, and A ₃/g _e β _e  = −0.972(2) mT, with the orientations of the g ₃- and A ₃-axes almost coaxial and perpendicular to the Al–O–Al plane; and those of the g ₁- and A ₁-axes approximately along the Al–Al and Al–OH directions, respectively. These results suggest that this aluminum-associated hole center represents hole trapping on a hydroxyl oxygen atom linked to two equivalent octahedral Al³⁺ ions, after the removal of the proton (i.e., a ^VIAl–O⁻–^VIAl center). Periodic ab initio UHF and DFT calculations confirmed the experimental ²⁷Al hyperfine coupling constants and directions, supporting the proposed structural model. The ^VIAl–O⁻–^VIAl center in jeremejevite undergoes the onset of thermal decay at 300 °C and is completely bleached at 525 °C. These data obtained from the ^VIAl–O⁻–^VIAl center in jeremejevite provide new insights into analogous centers that have been documented in several other minerals.