Strong site preference of Co2+ in olivine,Co1.10Mg0.90SiO4     

Subrata Ghose  Che'ng Wan 《Contributions to Mineralogy and Petrology》1974,47(2):131-140

The crystal structure and site preference of Co²⁺ in a synthetic Co_1.10Mg_0.90SiO₄ olivine have been determined from single crystal X-ray diffraction data collected on an automatic diffractometer. The R factor is 0.044 for 612 reflections. The site occupancies are: Ml site: Co 0.730±0.006; Mg 0.270; M2 site: Co 0.370, Mg 0.630. The Gibbs free energy change, ΔG° for the ion-exchange reaction between M1 and M2 sites is ?4.06 kcals/mole, assuming ideal mixing at each set of sites. This energy may be called ‘site preference energy’ of Co²⁺ in olivine. The strong preference of Co²⁺ for the M1 site can be quantitatively explained by two competing forces: preference of ions larger than Mg²⁺ for the M2 site and stronger covalent bonding of transition metal ions at the M1 site. For Fe²⁺, Mg²⁺, these two effects nearly neutralize each other, explaining the lack of considerable cation-ordering in Fe-Mg olivines.  相似文献   

Mössbauer spectroscopy: An introduction for inorganic chemists and geochemists: G. M. Bancroft. Halsted Press,New York,New York,xii + 252 pp., $21.50.1     

Subrata Ghose 《Quaternary Research》1974,4(2):232

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Cation distribution in low-calcium pyroxenes: Dependence on temperature and calcium content and the thermal history of lunar and terrestrial pigeonites     

Surendra K. Saxena  Subrata Ghose  A.C. Turnock 《Earth and Planetary Science Letters》1974,21(2):194-200

Four pyroxenes with compositions En₄₈Fs₄₈Wo₄, En_47·5Fs_47·5Wo₅, En₄₅Fs₄₅Wo₁₀ and En₄₀Fs₄₀Wo₂₀, synthesized at 1200°C at atmospheric pressure, were heat-treated at 500, 600, 700, and 800°C for various lengths of time. These pyroxenes are variously ordered with respect to Fe²⁺ and Mg²⁺ without unmixing. The Fe²⁺-Mg²⁺ distribution over the two nonequivalent sites M1 and M2, determined through Mössbauer spectroscopy, is found to be a function of both temperature and concentration of Ca²⁺ at the M2 site. The preference of Fe²⁺ for the M2 site increases with decreasing temperature and increasing Ca²⁺. These data can be used to determine cation equilibration temperatures of lunar and terrestrial pigeonites. The lunar pigeonites usually indicate equilibration temperatures of 700–860°C, except the pigeonite from rock 14053, which may have been subjected to shock heating due to meteoritic impact.  相似文献   

Direct observation of anti-phase domain structure in omphacite     

P. P. Phakey  Subrata Ghose 《Contributions to Mineralogy and Petrology》1973,39(3):239-245

Single crystal electron diffraction patterns of an omphacite (CaNa, Mg²⁺, Fe²⁺, Al³⁺, Fe³⁺)Si₂O₆ from a glaucophane schist facies (type C) eclogite, Tiburon Peninsula, California show weak reflections violating the C2/c space group. Transmission electron microscopy with dark field imaging, using h+k = even reflections reveal no special features, while dark field viewing through certain superstructure reflections violating the C2/c space group (h k l, with h+k = odd and h 0 l with h and/or l odd) reveal anti-phase domains, 100 to 3000 Å in width. Diffraction contrast experiments show that these domains are related by a displacement vector R=1/2[110]. This displacement vector explains the origin of the domains in terms of ordering of various cations in the octahedral (M1 type) and polyhedral (M2 type) sites without any changes in the tetrahedral silicate chains.  相似文献   

High temperature single crystal X-ray diffraction studies of the ortho-proto phase transition in enstatite,Mg2Si2O6 at 1360 K     

Hexiong Yang  Subrata Ghose 《Physics and Chemistry of Minerals》1995,22(5):300-310

A high temperature single-crystal X-ray diffraction study of enstatite, Mg₂Si₂O₆ was undertaken at 296, 900, 1200, 1360 and 1400 K. During the X-ray data collection at 1360 K (T₀), orthoenstatite (Pbca) transformed to protoenstatite (Pbcn). The unit cell parameters measured at T₀ are a=18.456(4), b=8.960(2) and c=5.270(1) Å for ortho and a=9.306(1), b=8.886(1) and c=5.360(1) Å for proto. The discontinuous increase in c and decrease in b due to the ortho to proto transformation are associated with the drastic unkinking of the silicate chains, whereas the abrupt increase in a results from the large expansion of the M2 — O distances along a coupled with the increase in the out-of-plane tilting of the silicate tetrahedra. Stacking faults form in ortho prior to the phase transition, as well as in proto between 1360 and 1400 K. With increasing temperature, the silicate B chain in ortho straightens faster than the A chain as the configurations of the SiA and SiB tetrahedra tend to become similar. At T₀, the A and B chains with the O3-O3-O3 angles (O3 being the bridging oxygen atom) of 163.0° and 149.5° in ortho, respectively, attain an identical angle of 168.4° in proto. The configuration of the silicate chain in proto resembles that of the A chain in ortho. Rigid-body thermal vibration analysis suggests that between 1200 and 1400 K the largest, the second largest and the smallest thermal librational motions of the [SiO₄] tetrahedra in both ortho and proto are approximately around a, c and b, respectively. Below 1200 K, the largest thermal librational amplitudes of the SiA and SiB tetrahedra in ortho are quite different, but become nearly equivalent at T₀. In contrast to the results reported for all iron-bearing orthopyroxenes at high temperature, switching of the O3B atoms coordinated with the M2 cation occurs during the ortho to proto transformation, but not in ortho below T₀. The ortho-proto transition does not affect the configuration of the M1 octahedron significantly, but results in a decrease of the mean M2 — O bond distance by 0.043 Å and a highly distorted M2 octahedron in proto.  相似文献   

Phase transitions in ilvaite,a mixed-valence iron silicate     

Subrata Ghose  Katsuhiro Tsukimura  Dorian M. Hatch 《Physics and Chemistry of Minerals》1989,16(5):483-496

Ilvaite, Ca(Fe²⁺, Fe³⁺) Fe²⁺Si₂O₇O(OH), a mixed-valence iron silicate shows an insulator-semimetal transition with a band gap of 0.13 eV due to thermally induced charge delocalization between Fe²⁺ and Fe³⁺ ions (A sites) in double octahedral chains. The charge delocalization induces a second order crystallographic phase transition on heating from monoclinic (P2₁/a) to orthorhombic (Pnam) symmetry at 346 K. The unit cell dimensions within the 295–420 K range and the crystal structures at 295, 320, 340, 360, 380 and 400 K have been determined by high temperature single crystal X-ray diffraction. The degree of charge delocalization determined from the sizes of the Fe(Ao) and Fe(Am) octahedra is the primary order parameter, Q which couples linearly with the spontaneous strain component, ₁₃. The order parameter coupling and the associated free energy expression is given. The calculated normal modes of the space group symmetry change are consistent with the experimentally observed atomic displacements, which are parallel and antiparallel to c. Formation of antiphase lamellar twin domains parallel to (001) in the monoclinic phase is predicted to occur as a result of the phase transition. Above T_c (= 346 K), the slow asymptotic decrease of ₁₃ attaining a zero value at 380 K indicates the presence of fluctuating precursor clusters with considerable short-range order above T_c. A peak in the specific heat (C_p) measurements coincides with the onset of longrange order at 380 K, whereas ⁵⁷Fe Mössbauer measurements indicate the onset of charge localization at a considerbly higher temperature (470 K). The coupling of the d⁶ electron of the Fe²⁺ (A) ion with a longitudinal optic phonon with the polarization vector along c ^* is the likely mechanism to drive the phase transition. The electronphonon coupling also provides a charge conduction mechanism through electron hopping, whereby the short-bonded Fe²⁺-Fe³⁺ pair containing the d⁶ electron (intermediate polaron) will break up and re-form, thereby propagating the electron one step along the c axis.  相似文献   

Magnetic order in acmite; NaFeSi2O6     

O. Ballet  J. M. D. Coey  G. Fillion  A. Ghose  A. Hewat  J. R. Regnard 《Physics and Chemistry of Minerals》1989,16(7):672-677

The magnetic properties of two samples of acmite, one natural and the other synthetic, were determined using magnetization and susceptibility measurements, Mössbauer spectroscopy and neutron diffraction. Exchange interactions are quite strongly antiferromagnetic, the paramagnetic Curie temperature being -46 K for a purely ferric synthetic sample, but its Néel temperature is only 8 K. The principal magnetic mode has the periodicity of the crystallographic structure and is made of ferromagnetic chains, coupled antiferromagnetically. Moments are oriented in a direction close to the chain axis, c. The antiferromagnetic exchange between adjacent Fe³⁺ ions in the same chain is overcome by their coupling to a common Fe³⁺ neighbour in the next chain. This indicates that the whole (SiO₄) group can act as a superexchange ligand in silicates.  相似文献   

Nuclear magnetic resonance of 7Li and 23Na in zektzerite,NaLiZrSi6O15     

Subrata Ghose  D. Brinkmann  J. Roos 《Physics and Chemistry of Minerals》1989,16(7):720-724

The electric field gradient (EFG) tensors of ⁷Li and ²³Na in a zektzerite, NaLiZrSi₆O₁₅ single crystal have been determined by the nuclear magnetic resonance technique. The quadrupole coupling constants, e²qQ/h and the asymmetry parameters, η, for ⁷Li are 119 ± 5 kHz, 0.05 and for ²³Na 2.42 ± 0.15 MHz, 0.86 respectively. In both cases, the EFG tensors show the two-fold site-symmetries at the Li- and Na-sites. For ⁷Li, the magnitude of the quadrupole coupling constant and the principal axis of the EFG tensor reflect the large angular distortion of the [LiO₄] tetrahedron. The large quadrupole coupling constant of ²³Na indicates a high degree of distortion of the Na coordination polyhedron.  相似文献   

Lattice dynamics and Raman spectroscopy of protoenstatite Mg2Si2O6     

Subrata Ghose  Narayani Choudhury  S. L. Chaplot  C. Pal Chowdhury  S. K. Sharma 《Physics and Chemistry of Minerals》1994,20(7):469-477

Enstatites (Mg₂Si₂O₆) are important rock forming silicates of the pyroxene group whose structures are characterised by double MgO₆ octahedral bands and single silicate chains. Orthoenstatite transforms to protoenstatite above 1273 K with a doubling of the a axis and a rearrangement of the silicate chains with respect to the Mg₂₊ ions. Lattice dynamical calculations based on a rigid-ion model in the quasi-harmonic approximation provide theoretical estimates of elastic constants, long wavelength phonon modes, phonon dispersion relations, total and partial density of states and inelastic neutron scattering cross-sections of protoenstatite. The computed elastic constants are in good agreement with experimental data. The computed density of states of a chain silicate such as protoenstatite is distinct from that of olivines (forsterite, Mg₂SiO₄ and fayalite, Fe₂-SiO₄) with isolated silicate tetrahedra. The band gaps in the density of states in forsterite are largely due to the separation in the frequency ranges of the external and internal vibrations of the isolated silicate group, whereas in protoenstatite these gaps are filled by the vibrations of the bridging oxygens of the silicate chain. The computed density of states is used to calculate the specific heat, the mean square atomic displacements and temperature factors. Validity of these calculations are supported by Raman scattering measurements. Polarised and unpolarised Raman spectra are obtained from small single crystals of protoenstatite (Li,Sc)_0.6Mg_1.4Si₂O₆ stable at room temperature using the 488 nm or 514.5 nm lines of an Ar⁺ ion laser and a micro-Raman spectrometer with backscattering geometry. The Raman spectra were analysed and interpreted based on the lattice dynamical model. The experimental Raman frequencies and mode assignments (based on polarised single crystal spectra) are in good agreement with those obtained from lattice dynamical calculations.  相似文献   

Development and application of Shannon’s entropy integrated information value model for landslide susceptibility assessment and zonation in Sikkim Himalayas in India     

Sharma  L. P.  Patel  Nilanchal  Ghose  M. K.  Debnath  P. 《Natural Hazards》2015,75(2):1555-1576

Natural Hazards - The state of Sikkim in India has many steep slopes and has been susceptible to landslides. Since 1968 there have been innumerable losses of lives and properties due to landslides....  相似文献