SCF-Xα-SW MO Study of Fe-O and Fe-OH chemical bonds; applications to the mössbauer spectra and magnetochemistry of hydroxyl-bearing Fe3+ oxides and silicates     

David M. Sherman 《Physics and Chemistry of Minerals》1985,12(5):311-314

Results of SCF-Xα-SW molecular orbital calculations on (FeO₄(OH)₂)^7? and (FeO₆)^9? clusters are used to investigate the differences between Fe-O and Fe-OH bonding in hydroxyl-bearing iron oxides and silicates. The Fe³⁺-OH^? bond is more ionic, and has a smaller spinpolarization, then the Fe³⁺-O^2? bond. The smaller spinpolarizability of OH^? ligands explains why superexchange interactions between hydroxo-bridged Fe³⁺ cations are much weaker than those between oxo-bridged Fe³⁺ cations. Replacement of oxygens in the Fe³⁺ coordination environment by OH^? ligands appears to promote the covalency between Fe³⁺ centers and O^2? oxygens. The increased covalency lowers the effective spin of the Fe atom. This, in turn, explains the decreased magnetic hyperfine fields at the Fe nucleus in FeOOH polymorphs relative to those found in Fe³⁺ oxides.  相似文献   

Crystal field and charge transfer spectrum of (Mg, Fe)SiO3 majorite     

Hans Keppler  Catherine A. McCammon 《Physics and Chemistry of Minerals》1996,23(2):94-98

Majorite of bulk composition Mg_0.86Fe_0.15SiO₃ was synthesized at 19 GPa and 1900 °C at an oxygen fugacity close to the Re/ReO₂ buffer. Optical absorption spectra of polycrystalline samples were measured from 4000 to 25000cm^?1. The following features were observed: (1) Three bands at 4554, 6005 and 8093 cm^?1 due to the ⁵E_g → ⁵T_2g transition of Fe²⁺ in a distorted dodecahedral site. (2) A band at 9340 cm^?1 due to the transition ⁵T_2g → ⁵E_g of octahedral Fe²⁺. (3) A band at 22784 cm^?1 resulting from Fe³⁺, probably in an octahedral site (⁶A_1g → ⁴A_1g, ⁴E_g). (4) A very intense system of Fe²⁺ → Fe³⁺ intervalence charge transfer bands which can be modelled by two Gaussian components centered at 16542 and 20128 cm^?1. The existence of two components in the charge transfer spectrum could be related to the fact that the tetragonal majorite structure may contain Fe³⁺ in two different octahedral sites. The crystal field splitting Δ of Fe²⁺ in dodecahedral coordination is 5717 cm^?1. If a splitting of the ground state in the order of 1000 cm^?1 is assumed, this yields a crystal field stabilization energy (CFSE) of 3930 cm^?1, comparable to the CFSE of Fe²⁺ in pyrope-rich garnet. However, the splitting of ⁵T_2g is significantly higher than in pyrope. This would be consistent with Fe²⁺ preferentially occupying the more distorted one of the two dodecahedral sites in the majorite structure. For octahedral Fe²⁺, Δ= 9340 cm^?1 and CFSE=3736 cm^?1, assuming negligible splitting of the ground state.  相似文献   

Dehydration experiments on natural omphacites: qualitative and quantitative characterization by various spectroscopic methods   总被引：1，自引：0，他引：1  

M. Koch-Müller  I. Abs-Wurmbach  D. Rhede  V. Kahlenberg  S. Matsyuk 《Physics and Chemistry of Minerals》2007,34(9):663-678

A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe²⁺ at M1 as well as at M2, and in a first approach assigned Fe³⁺ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ε _i,tot = 65,000 ± 3,000 lmol_H2O ^?1 cm^?2. Using this new ε _i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H₂O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe³⁺ (<0.1 Fe³⁺ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm^?1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al³⁺ at the tetrahedral site (OH bands around 3,525 cm^?1, Koch-Müller et al., Am Mineral, 89:921–931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe³⁺-rich sample (0.2 Fe³⁺ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm^?1 plus shoulder at 3,450 cm^?1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe³⁺ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe²⁺ and combined with increase in Fe³⁺. That dehydration is correlated with oxidation of Fe²⁺ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH^? content and giving no indication of Fe²⁺-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe²⁺ at M2 and low-water concentrations, i.e., at a ratio of Fe^{2+ M2}/H > 10 dehydration occurs by iron oxidation of Fe²⁺ exclusively at the M2 site following the reaction: \( {\left[ {{\text{Fe}}^{{{\text{2 + [ M2]}}}}{\text{OH}}^{ - } } \right]} = {\left[ {{\text{Fe}}^{{{\text{3 + [ M2]}}}} {\text{O}}^{{{\text{2}} - }} } \right]} + {\text{1/2}}\;{\text{H}}_{{\text{2}}} \uparrow . \) In samples having relatively low concentration of Fe²⁺ at M2 but high-water concentrations, i.e., ratio of Fe^{2+ M2}/H < 5.0 dehydration occurs through oxidation of Fe²⁺ at M1.  相似文献   

Crystal chemistry of volcanic allanites indicative of naturally induced oxidation-dehydrogenation     

Mihoko Hoshino  Mitsuyoshi Kimata  Craig A. Chesner  Norimasa Nishida  Masahiro Shimizu  Takeshi Akasaka 《Mineralogy and Petrology》2010,99(1-2):133-141

The crystal chemistry of volcanic allanites from both the Youngest Toba Tuff (YTT), Sumatra, Indonesia and SK100 volcanic ash beds (SK100-VAB), Niigata, Japan has been examined by electron microprobe analysis (EMPA), Fourier-transform infrared spectroscopic analysis (FTIR), and single-crystal structure analysis. In the FTIR study, based on the Diamond ATR accessory, YTT and SK100- VAB allanites were observed to have different OH contents, respectively: the former has 0.64 wt% H₂O (OH: 0.40 apfu.), while the latter has 1.65 wt% H₂O (OH: 1.00 apfu.). The crystal structures of these two allanites have been refined to individual R indices (3.64 and 4.25) based on 1350 observed reflections (|Fo| > 4sig|Fo|) measured using a single-crystal diffractometer with MoKα X-radiation. The OH-poor YTT allanite has a shorter b axis, a longer c axis, and larger β value than the relatively OH-rich SK100-VAB one. The bond valence sums of O4 (accepter oxygen for H atom) and O10 (donor oxygen for H atom) are 1.962 and 1.709 v.u. for YTT allanite (valence sum: 3.671 v.u.) and 1.754 and 1.271 v.u. for SK100-VAB one (valence sum: 3.025 v.u.). The difference from the ideal total bond valence value (4.00 v.u.) of O4 and O10 in YTT allanite (0.33 v.u.) is smaller than that in SK100-VAB (0.98 v.u.). These difference values are also broadly consistent with the corresponding differences in OH content between the YTT (OH: 0.40 apfu.) and SK100-VAB allanites (OH: 1.00 apfu.) determined by FTIR- ATR. Chemical analyses, FTIR-ATR and crystal structure refinement of YTT and SK100-VAB allanites yielded the following crystal chemical formula: YTT: (Ca_0.83Mn²⁺ _0.06Fe²⁺ _0.11)(La_0.24Ce_0.32Pr_0.04Nd_0.11Sm_0.02Th_0.04Ca_0.21)(Al_0.73Fe³⁺ _0.19Ti_0.08)(Al_0.89Fe³⁺ _0.11)(Fe²⁺ _0.22Fe³⁺ _0.62Mg_0.16)(SiO₄)Si₂O₇O_1.6(OH)_0.4, SK100-VAB: (Ca_0.81Fe²⁺ _0.13Mn²⁺ _0.06)(La_0.22Ce_0.34Pr_0.05Nd_0.13Sm_0.02Th_0.02Ca_0.22)(Al_0.76Fe³⁺ _0.19Ti_0.05)Al_1.00(Fe²⁺ _0.73Fe³⁺ _0.17Mg_0.10)(Si_0.96Al_0.04O₄)Si₂O₇O(OH). Therefore, it is concluded that welding of the Youngest Toba Tuff caused the following post-crystallization changes to occur in YTT allanite: oxidation of Fe²⁺ to Fe³⁺, release of H₂, and the concomitant replacement of OH^? by O^2?. These oxidation and dehydrogenation processes advanced during the welding to thereby produce oxyallanite. Oxyallanite had been reported only in laboratory studies where it was produced by heating natural allanite. Our report on natural oxyallanite suggests that it may be present in other welded silicic volcanic rocks as well.  相似文献   

Solubility of Fe2(OH)3Cl (pure-iron end-member of hibbingite) in NaCl and Na2SO4 brines     

Martin B. Nemer  Yongliang Xiong  Ahmed E. Ismail  Je-Hun Jang 《Chemical Geology》2011,280(1-2):26-32

Pure-iron end-member hibbingite, Fe₂(OH)₃Cl(s), may be important to geological repositories in salt formations, as it may be a dominant corrosion product of steel waste canisters in an anoxic environment in Na–Cl- and Na–Mg–Cl-dominated brines. In this study, the solubility of Fe₂(OH)₃Cl(s), the pure-iron end-member of hibbingite (Fe^II, Mg)₂(OH)₃Cl(s), and Fe(OH)₂(s) in 0.04 m to 6 m NaCl brines has been determined. For the reactionFe₂(OH)₃Cl(s) + 3H⁺ ? 3 H₂O + 2 Fe²⁺ + Cl^?,the solubility constant of Fe₂(OH)₃Cl(s) at infinite dilution and 25 °C has been found to be log₁₀ K = 17.12 ± 0.15 (95% confidence interval using F statistics for 36 data points and 3 parameters). For the reactionFe(OH)₂(s) + 2H⁺ ? 2 H₂O + Fe²⁺,the solubility constant of Fe(OH)₂ at infinite dilution and 25 °C has been found to be log₁₀ K = 12.95 ± 0.13 (95 % confidence interval using F statistics for 36 data points and 3 parameters). For the combined set of solubility data for Fe₂(OH)₃Cl(s) and Fe(OH)₂(s), the Na⁺–Fe²⁺ pair Pitzer interaction parameter θ_{Na⁺/Fe²⁺} has been found to be 0.08 ± 0.03 (95% confidence interval using F statistics for 36 data points and 3 parameters). In nearly saturated NaCl brine we observed evidence for the conversion of Fe(OH)₂(s) to Fe₂(OH)₃Cl(s). Additionally, when Fe₂(OH)₃Cl(s) was added to sodium sulfate brines, the formation of green rust(II) sulfate was observed, along with the generation of hydrogen gas. The results presented here provide insight into understanding and modeling the geochemistry and performance assessment of nuclear waste repositories in salt formations.  相似文献   

Crystal chemistry of a Mg-vesuvianite and implications of phase equilibria in the system CaO-MgO-Al2O3-SiO2-H2O-CO21     

J. W. VALLEY  D. R. PEACOR  J. R. BOWMAN  E. J. ESSENE  M. J. ALLARD 《Journal of Metamorphic Geology》1985,3(2):137-153

Abstract Chemical analysis (including H₂, F₂, FeO, Fe₂O₃) of a Mg-vesuvianite from Georgetown, Calif., USA, yields a formula, Ca_18.92Mg_1.88Fe³⁺_0.40Al_10.97Si_17.81- O_69.0.1(OH)_8.84F_0.14, in good agreement on a cation basis with the analysis reported by Pabst (1936). X-ray and electron diffraction reveal sharp reflections violating the space group P4/nnc as consistent with domains having space groups P4/n and P4nc. Refinement of the average crystal structure in space group P4/nnc is consistent with occupancy of the A site with Al, of the half-occupied B site by 0.8 Mg and 0.2 Fe, of the half-occupied C site by Ca, of the Ca (1,2,3) sites by Ca, and the OH and O(10) sites by OH and O. We infer an idealized formula for Mg-vesuvianite to be Ca₁₉Mg(MgAl₇)Al₄Si₁₈O₆₉(OH)₉, which is related to Fe^3+-vesuvianite by the substitutions Mg + OH = Fe³⁺+ O in the B and O(10) sites and Fe³⁺= Al in the AlFe site. Thermodynamic calculations using this formula for Mg-vesuvianite are consistent with the phase equilibria of Hochella, Liou, Keskinen & Kim (1982) but inconsistent with those of Olesch (1978). Further work is needed in determining the composition and entropy of synthetic vs natural vesuvianite before quantitative phase equilibria can be dependably generated. A qualitative analysis of reactions in the system CaO-MgO-Al₂O₃-SiO₂-H₂O-CO₂ shows that assemblages with Mg-vesuvianite are stable to high T in the absence of quartz and require water-rich conditions (XH₂O > 0.8). In the presence of wollastonite, Mg-vesuvianite requires very water-rich conditions (XH₂O > 0.97).  相似文献   

Octahedral-site Fe2+ quadrupole splitting distributions from Mössbauer spectroscopy along the (OH, F)-annite join     

D. G. Rancourt  J. Y. Ping  B. Boukili  J. L. Robert 《Physics and Chemistry of Minerals》1996,23(1):63-71

We have performed a detailed Mössbauer study of synthetic annites on the (OH, F)-join. Recently developed data treatment and spectral analysis methods were used to extract true intrinsic Fe²⁺ quadrupole splitting distributions (QSDs) that represent the most information that can be resolved from the spectra. The overall room temperature (RT) QSDs can be consistently interpreted in terms of four QSD contributions (or populations) centered at: QS_HH2.55 mm/s for Fe²⁺O₄(OH)₂ octahedra (cis and trans not resolved), QS_HF 2.35 mm/s for Fe²⁺O₄(OH)F octahedra (cis and trans not resolved), QS_cFF2.15 mm/s for cis-Fe²⁺O₄F₂ octahedra, and QS_tFF 1.5 mm/s for trans-Fe²⁺O₄F₂ octahedra. Each such contribution has a width ( 0.2 mm/s) caused by distortions of the octahedra. Minor contributions due to Fe²⁺O₅(OH) and Fe²⁺O₅F octahedra probably also contribute to the overall Fe²⁺ QSDs. The ferric iron spectral components were also characterized. Here, two distinct types of octahedral Fe³⁺ contributions are seen and interpreted as being due mainly to Fe³⁺O₅OH and Fe³⁺O₅F octahedra, respectively. Tetrahedral Fe³⁺ is seen only in the OH-annite end-member and the total Fe³⁺ content drops significantly on addition of F. On leave from: Department of Materials Physics, University of Science and Technology Beijing, 100083 Beijing, China  相似文献   

Mössbauer spectra of kyanite,aquamarine, and cordierite showing intervalence charge transfer     

Kathleen M. Parkin  Bruce M. Loeffler  Roger G. Burns 《Physics and Chemistry of Minerals》1977,1(3):301-311

The blue colors of several minerals and gems, including aquamarine (beryl, Be₃Al₂Si₆O₁₈) and cordierite (Al₃(Mg, Fe)₂Si₅AlO₁₈), have been attributed to charge transfer (CT) between adjacent Fe²⁺ and Fe³⁺ cations, while Fe²⁺→Ti⁴⁺ CT has been proposed for blue kyanites (Al₂SiO₅). Such assignments were based on chemical analyses and on polarization-dependent absorption bands measured in visible-region spectra. We have attempted to characterize the Fe cations in each of these minerals by Mössbauer spectroscopy (MS). In blue kyanites, significant amounts of both Fe²⁺ and Fe³⁺ were detected with MS, indicating that Fe²⁺→Fe³⁺ CT, Fe²⁺→Ti⁴⁺ CT, and Fe²⁺ and Fe³⁺ crystal field transitions each could contribute to the electronic spectra. In aquamarines, coexisting Fe²⁺ and Fe³⁺ ions were resolved by MS, supporting our assignment of the broad, relatively weak band at 16,100 cm^?1 in E∥c spectra to Fe²⁺→Fe³⁺ CT between Fe cations replacing Al³⁺ ions 4.6Å apart along c. A band at 17,500 cm^?1 in E⊥c spectra of cordierite is generally assigned to Fe²⁺ (oct)→Fe³⁺ (tet) CT between cations only 2.74 Å apart. However, no Fe³⁺ ions were detected in the MS at 293K of several blue cordierites showing the 17,500 cm^?1 band and reported to contain Fe³⁺. A quadrupole doublet with parameters consistent with tetrahedral Fe³⁺ appears in 77K MS, but the Fe³⁺/Fe²⁺ ratios from MS are much smaller than values from chemical analysis. These results sound a cautionary note when correlating Mössbauer and chemically determined Fe³⁺/Fe²⁺ ratios for minerals exhibiting Fe²⁺→Fe³⁺ CT.  相似文献   

Structure and Mössbauer spectroscopy of barbosalite Fe2+Fe3+ 2 (PO4)2(OH)2 between 80 K and 300 K     

G. J. Redhammer  G. Tippelt  G. Roth  W. Lottermoser  G. Amthauer 《Physics and Chemistry of Minerals》2000,27(6):419-429

Natural barbosalite Fe²⁺Fe³⁺ ₂ (PO₄)₂(OH)₂ from Bull Moose Mine, South Dakota, U.S.A., having ideal composition, was investigated with single crystal X-ray diffraction techniques, Mössbauer spectroscopy and SQUID magnetometry to redetermine crystal structure, valence state of iron and evolution of ⁵⁷Fe Mössbauer parameter and to propose the magnetic structure at low temperatures. At 298?K the title compound is monoclinic, space group P2₁/n, a _o ?= 7.3294(16)?Å, b _o ?=?7.4921(17)?Å, c _o ?=?7.4148 (18)?Å, β?=?118.43(3)°, Z?=?2. No crystallographic phase transition was observed between 298?K and 110?K. Slight discontinuities in the temperature dependence of lattice parameters and bond angles in the range between 150?K and 180?K are ascribed to the magnetic phase transition of the title compound. At 298?K the Mössbauer spectrum of the barbosalite shows two paramagnetic components, typical for Fe²⁺ and Fe³⁺ in octahedral coordination; the area ratio Fe³⁺/Fe²⁺ is exactly two, corresponding to the ideal value. Both the Fe²⁺ and the Fe³⁺ sublattice order magnetically below 173?K and exhibit a fully developed magnetic pattern at 160?K. The electric field gradient at the Fe²⁺ site is distorted from axial symmetry with the direction of the magnetic field nearly perpendicular to V_zz, the main component of the electric field gradient. The temperature dependent magnetic susceptibility exhibits strong antiferromagnetic ordering within the corner-sharing Fe³⁺-chains parallel to [101], whereas ferromagnetic coupling is assumed within the face-sharing [1?1?0] and [?1?1?0] Fe³⁺-Fe²⁺-Fe³⁺ trimer, connecting the Fe³⁺-chains to each other.  相似文献   

Crystallographic,Mössbauer and electrokinetic study of synthetic lipscombite     

R. Vochten  E. De Grave 《Physics and Chemistry of Minerals》1981,7(5):197-203

The transformation of vivianite and the direct synthesis starting from pure chemicals lead to the formation of lipscombite {Fe _x ²⁺ Fe _3?x ³⁺ [(OH)_3?x/(PO₄)₂]} with varying Fe²⁺/Fe³⁺ molar ratios. The influence of this ratio on the Mössbauer spectra, solubility, electrokinetic potential and infrared spectra has been studied. By means of Mössbauer spectroscopy, the distribution of the Fe²⁺ and Fe³⁺ ions between the octahedral sites I and II has been investigated. The unit cell dimensions have been determined from Guinier-Hägg X-ray diffraction patterns. The crystal system is tetragonal for synthetic lipscombite with a=5.3020±0.0005 Å and c=12.8800±0.0005 Å. Lipscombite has been found to show a negative and time-dependent zeta-potential which, moreover, is influenced by the pH of the suspension and the Fe²⁺/Fe³⁺ molar ratio. An explanation of the time-dependence of the zeta-potential on variations of solubility is proposed. Infrared absorption spectrum only is characterized by two absorption bands: v _OH(3,500 cm^?1) and v _P?O(1,100-960 cm^?1). The density at 25° C is determined in toluene as 3.36±0.01 g·cm^?3.  相似文献   

Magnetic behavior of trioctahedral micas with different octahedral Fe ordering     

Stefano Pini  Maria Franca Brigatti  Marco Affronte  Daniele Malferrari  Augusto Marcelli 《Physics and Chemistry of Minerals》2012,39(8):665-674

This contribution is finalized at the discussion of the magnetic structure of two samples, belonging to phlogopite–annite [sample TK, chemical composition ^IV(Si_2.76Al_1.24) ^VI(Al_0.64Mg_0.72 $ {\text{Fe}}_{1.45}^{2 + } $ Mn_0.03Ti_0.15) (K_0.96Na_0.05) O_10.67 (OH)_1.31 Cl_0.02] and polylithionite–siderophyllite joints [sample PPB, chemical composition ^IV(Si_3.14Al_0.86)^VI(Al_0.75Mg_0.01 $ {\text{Fe}}_{1.03}^{2 + } $ $ {\text{Fe}}_{1.03}^{3 + } $ Mn_0.01Ti_0.01Li_1.09) (K_0.99Na_0.01) O_10.00 (OH)_0.65F_1.35]. Samples differ for Fe ordering in octahedral sites, Fe²⁺/(Fe²⁺?+?Fe³⁺) ratio, octahedral composition, defining a different environment around Fe cations, and layer symmetry. Spin-glass behavior was detected for both samples, as evidenced by the dependency of the temperature giving the peak in the susceptibility curve from the frequency of the applied alternating current magnetic field. The crystal chemical features are associated to the different temperature at which the maximum in magnetic susceptibility is observed: 6?K in TK, where Fe is disordered in all octahedral sites, and 8?K in PPB sample, showing a smaller and more regular coordination polyhedron for Fe, which is ordered in the trans-site and in one of the two cis-sites.  相似文献   

Stabilization of complex ions by the crystal field: CO 3 2− , NO 3 − , O 3 − , [(OH)4]4−, [(OH)3F]4−, [(OH)2F2]4−     

André Julg  Yves Ozias 《Physics and Chemistry of Minerals》1985,12(5):307-310

According to Koopmans' theorem, only the electrons associated with molecular levels of negative energy are stable. Many ions which cannot exist in the isolated state because certain occupied levels are positive, become stable in crystals under the stabilization effect arising from the crystal field. As examples, we have studied CO ₃ ^2? in calcite, NO ₃ ^? in NaNO₃, and several natural limpurities: O ₃ ^? in fluorite, [(OH)₄]^4?, [(OH)₃F]^4? and [(OH)₂F₂]^4? in zircon and thorite, by means of the molecular self-consistent field, the crystal field being simulated by point charges. As expected, all the energies corresponding to the occupied levels are negative within the crystal field, contrary to what occurs in the isolated state. Informations concerning the structure and the size of the critical germ are obtained for CaCO₃ and NaNO₃.  相似文献   

Magnetic properties of sheet silicates; 1:1 layer minerals     

J. M. D. Coey  O. Ballet  A. Moukarika  J. L. Soubeyroux 《Physics and Chemistry of Minerals》1981,7(3):141-148

Three iron-rich 1:1 clay minerals, greenalite [Si₂]{Fe ₃ ²⁺ }O₅(OH)₄, berthiérine [Si, Al]₂{Fe², Mg, Fe³⁺, Al}₃ O₅(OH)₄ and cronstedtite [Si, Fe³⁺]₂{Fe²⁺, Fe³⁺}₃O₅(OH)₄ have been studied by Mössbauer spectroscopy, magnetization measurements and neutron diffraction to determine their magneticproperties. The predominant magnetic coupling is ferromagnetic for pairs of ferrous ions in the octahedral sheet, but antiferromagnetic for ferric pairs. The crystal field at Fe²⁺ sites in greenalite and berthiérine is effectively trigonal with an orbital singlet l _z=0 as ground state. These mainly ferrous minerals order magnetically at 17K and 9K respectively. The magnetic structure of greenalite consists of ferromagnetic octahedral sheets, with the moments lying in the plane, coupled antiferromagnetically by much weaker interplane interactions. The ratio of intraplane to interplane coupling is of order 50, so the silicate has a two-dimensional aspect, both structurally and magnetically. Although the overall magnetic order is established as antiferromagnetic by neutron diffraction, the magnetization curves resemble those of a ferromagnet because of the very weak interplane coupling. Cronstedtite orders antiferromagnetically around 10K. Moments within the planes are antiferromagnetically coupled. The magnetism has no particular two-dimensional character because exchange paths between the layers are provided by the ferric cations present in the tetrahedral sheets.  相似文献   

Mössbauer and infrared spectroscopic studies of Belgian chloritoids     

E. De Grave  R. Vanleerberghe  L. Verdonck  G. De Geyter 《Physics and Chemistry of Minerals》1984,11(2):85-94

Three chloritoid samples from the Stavelot massif (Belgium) and one sample from the Serpont massif (Belgium) have been characterized by chemical analyses and differential X-ray diffraction. A classification of chloritoid is proposed. Mössbauer spectra at temperatures between 78 and 360 K and in external magnetic fields were obtained for a triclinic and for a monoclinic specimen. The spectra show a superposition of a weak Fe³⁺ doublet (less than 10%) and an intense Fe²⁺ doublet. It is found that a decomposition of the ferrous absorption into two distinct quadrupole doublets leads to smaller deviations between experimental and calculated line shapes, especially at low temperatures. This suggests that Fe²⁺ is present in both cis and trans O₂(OH)₄ octahedral positions in the trioctahedral layer. However, the structural data derived from the temperature dependence of isomer shifts and quadrupole splittings, are found to be inconsistent with known crystallographic data. It is therefore concluded that Fe²⁺ is present in only one type of lattice site and that the numerically imposed decomposition into two ferrous doublets is merely an artifact due to thickness saturation effects and to the distributive character of the hyperfine parameters. The negative sign of the electric field gradient further confirms the assignment of the Fe²⁺ doublet to a cis octahedral configuration. Finally, only minor differences between the Mössbauer results for triclinic and monoclinic chloritoid are observed. The infrared absorption spectra of the four samples are almost identical except in the region around 600 cm^?1 at which the monoclinic phase exhibits two absorption bands instead of one band for the triclinic samples. All absorption bands can be well assigned to the different vibrations. Inter-layer hydrogen bonding is evidenced by the occurrence of two v _O-H absorption bands. Furthermore, the specific nature of the infrared spectra enables a fast identification of chloritoid samples.  相似文献   

Li-bearing, disordered Mg-rich tourmaline from a pegmatite-marble contact in the Austroalpine basement units (Styria, Austria)     

Andreas Ertl  Heinrich Mali  Ralf Schuster  Wilfried Körner  John M. Hughes  Franz Brandstätter  Ekkehart Tillmanns 《Mineralogy and Petrology》2010,99(1-2):89-104

Pale-blue to pale-green tourmalines from the contact zone of Permian pegmatites to mica schists and marbles from different localities of the Austroalpine basement units (Rappold Complex) in Styria, Austria, are characterized. All these Mg-rich tourmalines have small but significant Li contents, up to 0.29 wt% Li₂O, and can be characterized as dravite, with FeO contents of ?~?0.9–2.7 wt%. Their chemical composition varies from ^X (Na_0.67Ca_0.19?K_0.02?_0.12) ^Y (Mg_1.26Al_0.97Fe²⁺ _0.36Li_0.19Ti⁴⁺ _0.06Zn_0.01?_0.15) ^Z (Al_5.31?Mg_0.69) (BO₃)₃ Si₆O₁₈ ^V (OH)₃? ^W [F_0.66(OH)_0.34], with a?=?15.9220(3), c?=?7.1732(2) Å to ^X (Na_0.67Ca_0.24?K_0.02?_0.07) ^Y (Mg_1.83Al_0.88Fe²⁺ _0.20Li_0.08Zn_0.01Ti⁴⁺ _0.01?_0.09) ^Z (Al_5.25?Mg_0.75) (BO₃)₃ Si₆O₁₈ ^V (OH)₃? ^W [F_0.87(OH)_0.13], with a?=?15.9354(4), c?=?7.1934(4) Å, and they show a significant Al-Mg disorder between the Y and the Z sites (R1?=?0.013–0.015). There is a positive correlation between the Ca content and?<?Y-O?>?distance for all investigated tourmalines (r?≈?1.00), which may reflect short-range order configurations including Ca and Fe²⁺, Mg, and Li. The tourmalines have X_Mg (X_Mg?=?Mg/Mg?+?Fe_total) values in the range 0.84–0.95. The REE patterns show more or less pronounced negative Eu and positive Yb anomalies. In comparison to tourmalines from highly-evolved pegmatites, the tourmaline samples from the border zone of the pegmatites of the Rappold Complex contain relatively low amounts of total REE (~8–36 ppm) and Th (0.1–1.8 ppm) and have low La_N/Yb_N ratios. There is a positive correlation (r?≈?0.91) between MgO of the tourmalines and the MgO contents of the surrounding mica schists. We conclude that the pegmatites formed by anatectic melting of mica schists and paragneisses in Permian time. The tourmalines crystallized from the pegmatitic melt, influenced by the metacarbonate and metapelitic host rocks.  相似文献   

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

K. Langer  R. M. Abu-Eid 《Physics and Chemistry of Minerals》1977,1(3):273-299

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.  相似文献   

Optical absorption spectra and Fe distribution in the structures of Li-Fe micas     

A. N. Platonov  V. M. Khomenko  T. N. Shuriga 《Geochemistry International》2009,47(2):174-185

The paper proposes pioneering data on the polarized optical absorption spectra of Li-Fe micas: intermediate members of the siderophyllite-zinnwaldite-polylithionite and annite-protolithionite-zinnwaldite-trilithionite series with variable Fe and Li proportions and Li- and Fe-bearing muscovite (phengite). Based on the analysis of structural data, the complicated structure of the Fe²⁺ → Fe³⁺ charge transfer band in the mica structures is explained, and arguments are presented to justify the ascribing of its shortwave component (CTB-1, ν = 17200-14900 cm^?1) to charge transfer in the pair Fe²⁺(M2) → Fe³⁺(M2) and the longwave component (CTB-2, ν = 14200-13600 cm^?1) to charge transfer in the pair Fe²⁺(M1) Fe³⁺(M2). It is demonstrated that the anomalous shift of the superposition of two-component CTB toward the shortwave region, to 17000 cm^?1, results from a decrease in the length of oxygen edges between adjacent M2M2 and M1M2 tetrahedrons when Li is accommodated in the mica structure. The first data are presented on the spectrum of Fe²⁺ ions in large distorted M3(M1) tetrahedrons (OAC Fe²⁺ II) in hetero-octahedral Li micas (zinnwaldite), and the behavior of the corresponding absorption bands at 11400 and 8000 cm^?1 is determined. It is proved that characteristics of the optical spectra of Fe²⁺ ions can be used as an indicator of the structure of the octahedral layer in the mica structures. Results of the comparative analyses of spectral parameters of the Fe²⁺ → Fe³⁺ charge transfer, crystal field spectra of Fe²⁺ ions, and the crystal-chemical characteristics controlling them in micas of the polylithionite-siderophyllite series are completely consistent with the character of cation ordering in the crystal structures of these micas determined by X-ray diffraction analysis.  相似文献   

Crystal field spectra and jahn teller effect of Mn3+ in clinopyroxene and clinoamphiboles from India     

S. Ghose  M. Kersten  K. Langer  G. Rossi  L. Ungaretti 《Physics and Chemistry of Minerals》1986,13(5):291-305

Blanfordite (I), winchite (II), and juddite (III), all showing vivid colors and pleochroism, from highly oxidized parageneses of Indian gondites were studied by microprobe, Mössbauer, and microscope-spectrophotometric techniques and by X-ray structure refinements. The compositions of the Mn-bearing minerals were close to diopsideacmite (I) and magnesio-arfvedsonite to magnesio-riebeckite (II and III). Transition metal ions are located inM(1)-octahedra (I) or predominantlyM(2)-octahedra (II, III). Mössbauer spectra of⁵⁷Fe(IS, ΔE _Q) are typical of octahedral Fe³⁺ only. Polarized absorption spectra in the UV/VIS/NIR ranges explain color and pleochroism of the minerals. The position of the UV-“edge” is correlated with Fe³⁺-contents of the minerals, except for judditeE ∥Z, where the edge shows an unusual low energy position. This is most likely due to Mie-scattering of submicroscopic inclusions of braunite with nearly uniform dimensions. In the VIS range, the spectra are dominated by a complex band system between 15,000 and 20,000 cm^?1. Energies and ?-values of component bands are compatible with those of Mn³⁺ d-d transitions in other Mn³⁺-bearing silicates. The polarization behavior of component bands can best be explained by aC ₂(C2″) symmetry of the crystal field. The Jahn-Teller splitting (<9,000 cm^?1) of the⁵ E _g ground state of Mn³⁺ inO _h crystal fields is appreciably smaller than in other Mn³⁺-silicates. Crystal field parameters 10Dq, (I) 13,650, (II) ca. 11,640, and (III) 11,925 cm^?1, are near to that in piemontite. The crystal field stabilization energy of Mn³⁺, (I) 146, (II) ca. 140, (III) 142 \({{{\text{kJ}}} \mathord{\left/ {\vphantom {{{\text{kJ}}} {\text{g}}}} \right. \kern-0em} {\text{g}}}{\text{ - atom}}_{{\text{Mn}}^{{\text{3 + }}} } \) , is appreciably smaller than that found in other Mn³⁺-silicates (piemontites and manganian andalusites, viridines and kanonaite).  相似文献   

Phase transitions in ilvaite,a mixed-valence iron silicate I. A 57Fe Mössbauer study of magnetic order and spin frustration     

Kan Xuemin  Subrata Ghose  B. D. Dunlap 《Physics and Chemistry of Minerals》1988,16(1):55-60

Ilvaite, Ca(Fe²⁺,Fe³⁺)Fe²⁺Si₂O₈(OH) shows two magnetic phase transitions, which have been studied by Mössbauer spectroscopy within the temperature range 120–4 K. The continued charge localization between Fe²⁺ and Fe³⁺ ions in octahedral A-sites causes the Fe²⁺-Fe³⁺ interaction to be ferromagnetic, although the overall magnetic order is antiferromagnetic. The thermal evolution of the hyperfine fields at the Fe²⁺ (A) and Fe³⁺ (A) sites indicates B _hf: 328 and 523 kOe respectively at 0 K and T _N1= 116K. The corresponding values for Fe²⁺ (B) site are: B _hf 186 kOe and T _N2=36K. An additional hyperfine field exists at the Fe²⁺(B) site within the temperature range 116–36K due to short-range order induced by the spin ordering in A sites. The considerable difference between the two magnetic transition temperatures is due to spin frustration, because the Fe²⁺ (B) site occurs on a corner common between two triangles with respect to two sets of Fe²⁺ (A) and Fe³⁺ (A) sites with opposite spin directions.  相似文献   

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

Davide Lenaz  Vanni Lughi 《Physics and Chemistry of Minerals》2013,40(6):491-498

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