Theoretical investigations of the spin Hamiltonian parameters and local angular variations for the trigonal V3+ centers in alum compounds

The spin Hamiltonian parameters (zero-field splittings D, g factors g _// and g _⊥) for V³⁺ in the alum compounds are theoretically studied using the perturbation formulas for these parameters for a 3d² ion in the trigonally distorted octahedra. The contributions from the dynamical Jahn–Teller effect, the configuration interactions and the ligand orbital and spin–orbit coupling interactions are considered from the cluster approach in a uniform way. The angles in the deformed octahedra around V³⁺ ions are increased by 1.1°–2.7°, as compared with those ones for the host. The theoretical spin Hamiltonian parameters based on the above angular variations and the related effects show good agreement with the experimental data, which reveal that these effects (especially the Jahn–Teller effect) can bring forward significant influences on the spin Hamiltonian parameters, and should be taken into account in electron paramagnetic resonance (EPR) analysis. The contributions from the configuration interactions and the ligand orbital and spin–orbit coupling interactions are quantitatively involved from the cluster approach in a uniform way. The results are discussed.     

EPR of V4+ and Fe3+ in titanites

EPR investigations of yellow-green titanites from four localities showed presence of V⁴⁺ and Fe³⁺. They were investigated at X-band and room temperature. For V⁴⁺ the principal values of the g matrix and ⁵¹V hyperfine splitting and the directions of their principal axes indicate presence of a VO²⁺ ion substituting for Ti. Due to a high zero-field splitting only approximate values of the fine structure parameters of Fe³⁺ could be determined. With directions of their principal axes very similar to those of V⁴⁺ this ion must also substitute for Ti. Unusually large linewidths for both ions with little variation for samples from different localities are ascribed to the reported domain structure of titanites and accumulation of impurities in the domain boundaries. While for Fe³⁺ a small variation of the fine structure parameters explains this broadening, for V⁴⁺ a distribution of g-factors equal to its total anisotropy must be responsible whereas the V=0 bond length is remarkably constant. Due to preferential incorporation of impurities in the grain boundaries a contribution of dipolar broadening cannot be excluded.     

Characterization and origin of two Fe3+ EPR spectra in kaolinite

The electron paramagnetic resonance (EPR) spectra of Fe³⁺ in a well cristallized kaolinite from Decazeville in France are well resolved. It is shown that in this sample there are mainly two slightly different spectra, well separated at low temperature and characterized at -150° C by the constants B ₂ ⁰ = 0.112 cm^?1, B ₂ ² = 0.0688 cm^?1 for one and B ₂ ⁰ = 0.116 cm^?1, B ₂ ² = 0.0766 cm^?1 for the second. These two spectra arise from Fe³⁺ substituted for Al³⁺ at the two octahedral positions in equal amounts. The temperature dependence of EPR spectra was studied and was explained by a modification of the octahedral sites.     

Studies on the spin Hamiltonian parameters and local structure for Rh4+ and Ir4+ in TiO2

The spin Hamiltonian (SH) parameters (g factors g _x , g _y and g _z and the hyperfine structure constants A _x , A _y and A _z ) and local structure for the rhombic Rh⁴⁺ and Ir⁴⁺ centers in TiO₂ (rutile) are theoretically studied from the perturbation formulas of these parameters for a low spin (S = 1/2) d ⁵ ion under rhombically distorted octahedra. In the calculations, the ligand orbital and spin–orbit coupling contributions as well as the influence of the local lattice distortions are taken into account using the cluster approach. The local axial elongation ratios are found to be about 1.7 and 3 times, respectively, larger for the Rh⁴⁺ and Ir⁴⁺ centers than that (≈0.0075) for the host Ti⁴⁺ site in rutile, while the perpendicular distortion angles (≈−0.28° and −0.42°, respectively) are more than one order in magnitude smaller than the host value (≈−9.12°). This means that the impurity centers exhibit further elongations of the oxygen octahedra and much smaller perpendicular rhombic distortions as compared with those of the host Ti⁴⁺ site in TiO₂. The above local lattice distortions can be mainly ascribed to the substitution of the host Ti⁴⁺ by the nd ⁵ impurities, which may induce different physical and chemical properties for the metal–ligand clusters. In addition, the influence of the Jahn–Teller effect on the local structure may not be completely excluded. The calculated SH parameters show reasonable agreement with the observed values.     

An EPR study of Mn2+ and Fe3+ in dolomites

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

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

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

Hyperfine interactions and spin transfer between Cr3+ and Al3+ in a synthetic single crystal of Mg2SiO4. A theoretical approach to the interpretation of EPR data

The occurrence of Cr-Al pairs in Mg₂SiO₄ has been detected by EPR spectroscopy. In the case where Cr³⁺ replaces Mg at the M2 position three different neighboring Si sites may be substituted by Al³⁺, which should yield different superhyperfine interactions. A new spectrum is presented which shows the presence of two of these possible pair configurations. An assignment of the spectral features to a specific Cr-Al pair with Cr at M2 from the experimental data alone was not possible, therefore, MSX _α cluster calculations have been performed from which the differences in the superhyperfine interaction for the various pair configurations could be obtained. Best agreement with the data of the Cr³⁺(M2)-Al pair exhibiting the most intense group of lines in the EPR spectrum was obtained for the situation where Al³⁺ is at the Si position with the shortest distance to M2. The second observed Cr³⁺(M2)-Al pair, which is significantly weaker in intensity, could not yet be assigned.     

Spectral source parameters for weak local earthquakes in the Pannonian basin

Dynamic source parameters are estimated from P-wave displacement spectra for 18 local earthquakes (1.2 < M_L < 3.7) that occurred in two seismically active regions of Hungary between 1995 and 2004. Although the geological setting of the two areas is quite different, their source parameters cannot be distinguished. The source dimensions range from 200 to 900 m, the seismic moment from 6.3x10¹¹ to 3.48×10¹⁴ Nm, the stress drop from 0.13 to 6.86 bar, and the average displacement is less than 1 cm for all events. The scaling relationship between seismic moment and stress drop indicates a decrease in stress drop with decreasing seismic moment. A linear relationship of M _w = 0.71 M _L + 0.92 is obtained between local magnitude and moment magnitude.     

Evaluation of rock-mass state in Polish copper mines through monitoring the borehole deformations

Sensors for borehole deformation measurements in mining panel roofs, as well as a method of high-energy tremors risk evaluation, based on borehole deformation monitoring are described. There are differences in manners in which borehole deformation takes place prior to a high-energy tremor. A method for rock-mass instability detection in copper mining panels is developed and described, as well as a practical procedure for forecasting the rock-mass state. On the basis of 1351 “real time” forecasts made in the 10 copper mine panels during 5451 days and on the basis of the 55 high-energy tremors occurred, the evaluation of forecast effectiveness is presented. The mean chance value of occurrence of the high-energy tremor after a rock-mass stability forecast was evaluated as 1% and after a rock-mass instability forecast, as 20%.     

Variation in si4+-content of phengites through a three stage deformation sequence

Three important phases of deformation (D₁-D₃) affect the Precambrian metamorphic rocks of the Strathgordon region, S.W. Tasmania. Textural analysis has related phengite development to the deformation events in quartz + phengite phyllites. Phengite chemistry suggests a prograde metamorphic history at about 4 kb from 400°C at D₁ to 450°C at D₂. The significant feature of this work is that a sharp break in conditions, shown by a marked change in the composition of the phengites, occurs from D₂ to D₃, the latter taking place at about 250°C and at a pressure <4 kb. A pronounced hiatus in the deformation history is indicated for the D₂/D₃ interval. During D₃ water was introduced.     

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

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

Estimation of the spatial distribution of ground motion parameters for two recent earthquakes in Japan

A recent development in strong motion instrumentation in Japan provides an opportunity to collect valuable data sets, especially after moderate and large magnitude events. Gathering and modeling these data is a necessity for better understanding of regional ground motion characteristics. Estimations of the spatial distribution of earthquake ground motion plays an important role in early-stage damage assessments for both rescue operations by disaster management agencies as well as damage studies of urban structures. Subsurface geology layers and local soil conditions lead to soil amplification that contributes to the estimated ground motion parameters of the surface. We present a case study of the applicability of the nationally proposed GIS-based soil amplification ratios [J. Soil Dyn. Earthqu. Eng. 19 (2000) 41–53] to the October 6, 2000 Tottori-ken Seibu (western Tottori Prefecture) and the March 24, 2001 Geiyo earthquakes in Japan. First, ground motion values were converted to those at a hypothetical ground base-rock level (outcrop) using an amplification ratio for each 1×1 km area, based on geomorphological and subsurface geology information. Then a Kriging method, assuming an attenuation relationship at the base-rock as a trend component, is applied. Finally, the spatial distribution of ground motion at ground surface is obtained by applying GIS-based amplification factors for the entire region. The correlation between the observed and estimated ground motion values is reasonable for both earthquakes. Thus, the proposed method is applicable in near real-time early-damage assessments and seismic hazard studies in Japan.     

Effect of Fe3+-bearing point defects on the UV-spectra of two natural olivines

Polarized near-UV spectra have been recorded on 20 μm diameter spots on oriented crystals of microprobe-analyzed olivines from Baikhal Rift, Fa_8.8 (I) and Seberget, Fa_9.3 (II), which have formed under different fO₂ and, therefore, are expected to contain Fe³⁺-bearing point defects in different concentrations. These should be reflected in the UV-spectra of such minerals (Cemic et al. 1986). The spectra obtained confirm these predictions: The difference in α _{Y, 26500} in both samples indicates a difference in Fe³⁺-site fractions of ΔX_Fe. = 1.78-10⁻⁴, which may be related to an fO₂ about ten times higher for the formation of olivine II compared to I.     

P-T grids for silica-undersaturated granulites in the systems MAS (n+ 4) and FMAS (n+ 3)-tools for the derivation of P-T paths of metamorphism

Abstract Considering the minerals cordierite (Cd), sapphirine (Sa), hypersthene (Hy), garnet (Ga), spinel (Sp), sillimanite (Si) and corundum (Co) in the system FeO-MgO-Al₂O₃-SiO₂ (FMAS), the stable invariant points are [Co], [Ga], [Cd] and [Sa]. Constraints imposed by experimental data for the system MAS indicate that under low P _H2o conditions the invariant points occur at high temperature (> 900° C) and intermediate pressure (7-10 kbar). This temperature is higher than that commonly advocated for granulite facies metamorphism. In granulites Fe-Mg exchange geothermometers may yield temperatures of 100–150° C below peak metamorphic conditions and evidence for peak temperatures is best preserved by relict high-temperature assemblages and by Al-rich cores in orthopyroxene. Application of the FMAS grid to some well-documented granulite occurrences introduces important constraints on their P-T histories. Rocks of different bulk compositions, occurring in close proximity in the field, may record distinct segments of their P-T paths. This applies particularly to rocks with evidence for reaction in the form of coronas, symplectites and zoned minerals. Consideration of curved reaction boundaries and _XMs isopleths may explain apparently contradictory results for the stability of cordierite obtained from low-temperature experiments and thermochemical calculations on the one hand and hightemperature experimental data on the other.     

Calculation of NMR parameters for bridging oxygens in H3T—O—T′H3 linkages (T,T′=Al,Si, P), for oxygen in SiH3O−, SiH3OH and SiH3OMg+ and for bridging fluorine in H3SiFSiH 3 +

Variations in the ¹⁷O nuclear quadrupole coupling constant, NQCC, and the ¹⁷O NMR shielding constant, σ^O, are evaluated for bridging oxygens in H₃T-O-T′H₃ linkages (with T, T′=Al, Si, P), and for nonbridging O in SiH₃O^?, SiH₃OH and SiH₃OMg⁺ and the ¹⁹F NMR shielding constant, σ^F, is evaluated for bridging F in H₃SiFSiH ₃ ^? using Hartree-Fock methods with large, flexible Gaussian basis sets. Trends in ¹⁷O NQCC as a function of T and T′ identity agree with experiment but the value for the Si-O-Al case is underestimated, indicative of neglected contributions from charge compensating cations. For H₃SiOSiH₃ the decrease in NQCC over the range from 180° to 140° is substantial but somewhat slower than the variation of -cosSi and σ^O decrease as Si of the nonbridging oxygen of SiH₃O^? compared to the bridging oxygen of H₃SiOSiH₃ but the calculated σ^Si in H₃SiOAlH ₃ ^? is too large and σ^O too small, indicative of important contributions from counter ions. By contrast, σ^O for PH₃OAlH₃ compared to SiH₃OSiH₃ is consistent with experiment. In H₃SiFSiH ₃ ⁺ (a model for bridging F in amorphous Si:H:F) the value of σ^Si is smaller and the NQCC at F is considerably larger than for H₃SiF, suggesting distinctive ²⁹Si and ¹⁹F NMR spectra for this species.     

Temperature dependence of intersite distribution of Mg and Fe in olivine and the associated change of lattice parameters

The cation distribution of natural and heated ferromagnesian olivine with chemical composition, Fo₆₇Fa₃₃, from metagabbro was examined by X-ray diffraction. Heating and quenching experiments were made by a newly devised apparatus which enables us to obtain very fast quenching speed in comparison with the usual technique. The distribution constants, K _D=(Fe⁺²/Mg) _M1/(Fe⁺²/Mg) _M2, of the natural samples were less than 1.07, and those of heat-treated samples were more than 1.15, indicating that cation ordering takes place with temperature. The distribution of Fe⁺² and Mg is nearly random at low temperatures, whereas Fe⁺² shows a slight but significant preference for a smaller M1 site at high temperatures. The change of the distribution constant was observed on specimens which were heated for a short period of time (6–1,060 s) and quenched within 10 ms. Thus the rate of the cation reordering reaction is a very fast process. The lattice parameters b and c decrease whereas a increases with the increase of distribution constant. The overall effect on unit cell volume is a decrease with the increasing distribution constant, suggesting the presence of significant pressure dependence of the cation distribution towards the ordering of Fe at M1 site in ferromagnesian olivine.