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1.
The temperature dependence of the lattice parameters of pure anorthite with high Al/Si order reveals the predicted tricritical behaviour of the \(I\bar 1 \leftrightarrow P\bar 1\) phase transition at T c * =510 K. The spontaneous strain couples to the order parameter Q° as x iS xQ i 2 with S xQ 1 =4.166×10?3, S xQ 2 =0.771×10?3, S xQ 3 =?7.223×10?3 for the diagonal elements. The temperature dependence of Q° is $$Q^{\text{o}} = \left( {1 - \frac{T}{{510}}} \right)^\beta ,{\text{ }}\beta = \tfrac{{\text{1}}}{{\text{4}}}$$ A strong dependence of T c * , S xQ i and β is predicted for Al/Si disordered anorthite.  相似文献   

2.
The borate polyhedra BO 3 3? , B(OH)3, BO 4 5? , and B(OH) 4 ? are studied using the ab initio and multiple scattering Xα quantum mechanical methods. The ab initio self-consistent-field (SCF) molecular orbital (MO) method, at the minimum basis set level, predicts equilibrium B-O distances within 0.04 Å of their average values in solids so long as the polyhedron charge is small. Orbital energies from double zeta basis set ab initio calculations and analogies with isoelectric compounds are used to assign the X-ray spectra of BO 3 3? and to predict the valence region spectra of BO 4 5? . Contour maps of the difference between molecular and superimposed free atom electron densities show charge buildup along the B-O bond which is only slightly smaller than that observed in CO 3 2? .  相似文献   

3.
The results of long-term photometric observations of R CrB in the UBV JHKLM bands are presented. The temporal and color characteristics of the emission of the star itself and of its extended dust envelope are analyzed in detail. No stable harmonic has been found in the semiregular variations of the optical brightness of R CrB. Two harmonics with periods P≈3.3 and 11.3 yrs have been detected in the brightness variations of the dust envelope; the minima of these variations coincided in 1999, resulting in a record decrease in the LM brightness of the envelope. This by chance coincided in time with a deep minimum of the visual brightness of the star, resulting in a unique decrease in the total brightness of the star and dust envelope. This enabled estimation of the bolometric flux of the hot dust clouds, which made up only a few per cent of the bolometric flux of the dust envelope. The brightness variations of the dust envelope are not accompanied by appreciable color changes and are associated with variations of its optical depth τ(V) in the range 0.2–0.4. The dust envelope forms at a large and fairly constant distance from the star $(r_{in} \approx 110R_* ,T_{gr} \approx 860 K)$ , from material in its stellar wind, whose intensity $(\dot M_{gas} \approx 2.1 \times 10^{ - 7} M_ \odot /year)$ obeys a Reimers law. No variations synchronous with those of the optical depth of the dust envelope, in particular, with the period P≈3.3 yrs, have been found in the optical emission of R CrB, suggesting that the stellar wind is not spherically symmetric. The dust envelope consists of small grains (a gr≤0.01 µm), while the clouds screening the star from the observer are made up of large grains (a gr≈0.1 µm). The activity of R CrB, whose nature is unclear, is reflected in variations of the stellar-wind intensity and the appearance of dust clouds in the line of sight: these variations are repeated by corresponding changes in the optical depth of the dust envelope with a delay of ~4 years (the time for a particle moving at V env≈45 km/s to move from the star to the boundary of the dust envelope).  相似文献   

4.
Electric dipole polarizabilities have been calculated from first principles of quantum mechanics for the BO 3 3? , CO 3 2? , NO 3 ? series and for NO 2 ? and LiNO3(g). Calculated trends in average polarizability and polarizability anisotropy in the BO 3 3? -NO 3 ? series are in agreement with experiment and can be qualitatively interpreted in terms of the varying energies of the a1′, a2″ and e′ symmetry unoccupied MO's of the oxyanions. Embedding a CO 3 2? ion in a D3h symmetry array of divalent cations reduces both the average polarizability and its anisotropy, particularly when diffuse s and p functions are included in the calculation. Calculations on the gas phase LiNO3 molecule and on the free NO 3 ? ion in the distorted geometry found in LiNO3(g) allow us to separate polarizability contributions internal to the NO 3 ? and Li+ ions from those which arise from the Li+-NO 3 ? interaction. The Li+-NO 3 ? interaction term so obtained is much smaller than the NO 3 ? contribution but is in turn larger than the Li+ contribution, suggesting that the inclusion of this interaction term is essential for obtaining accurate results for ion pairs. Although static polarizabilities are in reasonable agreement with experiment for NO 3 ? the wavelength dispersion of the polarizability is underestimated by about a factor of two, apparently as a result of inadequacies in the quantum mechanical method. Calculated values are also presented for 14N NMR shieldings in the nitrogen oxyanions but these are in only qualitative agreement with the experimental values. Similarly, calculated values of magnetic susceptibility are in only qualitative agreement with experiment although trends along the BO 3 3? -NO 3 ? series are properly reproduced.  相似文献   

5.
Hydrotalcite-like solid solutions have been synthesized by coprecipitation in basic solutions with variable SO 4 2? /CO 3 2? ratios. Chemical determination of CO 3 2? in the interlayer was impossible because of the presence of minor hydromagnesite. SO 4 2? was determined both by chemical analysis and X-ray photoelectron spectroscopy (XPS), the two methods giving similar results. A Raman spectrometry gave additional data on the SO 4 2? /CO 3 2? ratio. Then, the stoichiometry of the anionic interlayers, X s , X c , and X OH were determined, and the influence of X s on the c′ parameter (increasing from c′=7.97 Å to c′=8.63 Å between X s =0 and X s =1) was characterized. In addition, a partitioning curve of SO 4 2? and CO 3 2? between aqueous solutions and hydrotalcite-like compounds was established. Its general shape strongly suggests a miscibility gap between a sulfate-rich end and a carbonate-rich solid solution (maximum SO 4 2? /CO 3 2? about 0.2). This result explains why most of the hydrotalcites synthesized during experimental alteration of basaltic glasses by sea-water (a sulfate-rich solution) are CO 3 2? -rich solid solutions.  相似文献   

6.
The Xihuashan tungsten deposit (South Jiangxi, China) is located on the border of a granitic stock composed of four intrusive units: γ inf2a sup5 , γ inf2b sup5 , γ inf2c sup5 and γ inf2e sup5 chronologically. The deposit is situated in γ inf2a sup5 and γ inf2b sup5 whose contact zone is marked by a stockscheider and by a sporadic fine-grained granite designated γ inf2b′ sup5 . The feldspathic episyenitic veins or masses located mainly in γ inf2b sup5 resulted from granite alteration. This alteration characterizes the fluid activity which followed previous mechanical action, remnant liquids draining under structural control. The quartz-bearing Xihuashan veins (Dayu mining district) are a typical wolframite-quartz vein deposit and have developed mainly in γ inf2b sup5 . The density of the veins and the huge mineralizations in γ inf2b sup5 can be explained by the carapace role played by γ inf2a sup5 , γ inf2b′ sup5 and the stockscheider. The deposit is formed by 615 economically valuable veins (medium grade: 1,08% in WO3) characterized by four stages of mineralization; a reverse vertical zoning is generally observed. Thus, the Xihuashan tungsten deposit possesses a metallogenic value contributing to the comprehension of metallogenic and structural phenomena related to the evolution of granitic masses.  相似文献   

7.
Absorption bands are determined in polarized optical spectra of vivianite Fe3(PO4)2·8H2O, recorded at room and low temperatures. These bands are caused by spin-allowed d-d transitions in structurally nonequivalent Fe A 2+ (~11000 cm-1 (γ-polarization) (and) ~12000 cm-1 (β-polarization)) (and) Fe B 2+ (~8400 cm-1 (γ, α-polarization) and ~11200 cm-1 (α-polarization)) ions. A charge transfer band (CTB) Fe B 2+ +Fe B 3+ →Fe B 2+ +Fe B 2+ (~15000 cm-1) also determined, has polarizing features giving evidence of a change in the Fe B 2+ -Fe B 3+ bond direction, when compared with Fe B 2+ -Fe B 2+ . Bands of exchange-coupled Fe3+-Fe3+ pairs (~19400, ~20400, ~21300 and ~21700 cm-1) which appear on oxidation of Fe2+ in paired Fe B octahedra are also characterized.  相似文献   

8.
This paper presents the point-defect thermodynamics for fayalite and olivine solid solutions (Fe x Mg1?x )2SiO4. By means of thermogravimetry, the metal-to-oxygen ratio of these silicates has been determined as a function of oxygen potential, compositionx and temperature. Experiments were performed in the range of 1,000° C≦T≦1,280° C and 0.2≦x≦1.0. It is found that V Me , Fe Me · and the associate {Fe′ Si Fe Me · } are the majority defects. With this knowledge it is possible to calculate the nonstoichiometry at given temperature as a function of \(p_{O_2 } \) and \(a_{SiO_2 } \) . The cation vacancy concentration shows a \(p_{O_2 }^{1/5} \) -dependence (forx≧0.2) and increases at givenT and \(p_{O_2 } \) almost exponentially with compositionx. In the composition range studied here, the silicates show an oxygen excess, and FeO is more soluble in the olivine than SiO2.  相似文献   

9.
The observed properties of Wolf-Rayet stars and relativistic objects in close binary systems are analyzed. The final masses M CO f for the carbon-oxygen cores of WR stars in WR + O binaries are calculated taking into account the radial loss of matter via stellar wind, which depends on the mass of the star. The analysis includes new data on the clumpy structure of WR winds, which appreciably decreases the required mass-loss rates $\dot M_{WR}$ for the WR stars. The masses M CO f lie in the range (1–2)M –(20–44)M and have a continuous distribution. The masses of the relativistic objects M x are 1–20M and have a bimodal distribution: the mean masses for neutron stars and black holes are 1.35 ± 0.15M and 8–10M , respectively, with a gap from 2–4M in which no neutron stars or black holes are observed in close binaries. The mean final CO-core mass is $\overline M _{CO}^f = 7.4 - 10.3M_ \odot$ , close to the mean mass for the black holes. This suggests that it is not only the mass of the progenitor that determines the nature of the relativistic object, but other parameters as well-rotation, magnetic field, etc. One SB1R Wolf-Rayet binary and 11 suspected WR + C binaries that may have low-mass companions (main-sequence or subgiant M-A stars) are identified; these could be the progenitors of low-mass X-ray binaries with neutron stars and black holes.  相似文献   

10.
Exchange-mineral equilibria with Al and Fe3+ aqueous chloride solutions (aq.), Andr + AlCl aq 3 = FeCl aq 3 + Gros, (1) Psc + AlCl aq 3 = FeCl aq 3 + Czo, (2) were studied under the following experimental conditions: 500°;C and 580°;C and 1 and 2 kbar, respectively, with an overall concentration of metals in the aqueous solutions of about 0.5 M and pH 3. The mixing functions of the components in garnet and epidote were calculated from the experimental data. Thermodynamic treatment of experimental evidence for reaction (1) led to the conclusion that, within the accuracy of experiment, garnet in the andradite-grossularite series was an ideal solid solution. However, epidote solid solution markedly departed from the ideal, as was shown by concentration and pressure-temperature (PT) dependencies of Gibbs's molar excess energies and by mixing-volume concentration dependence.  相似文献   

11.
We present spectrophotometric (3400–7500 Å) observations of the evolution of a strong outburst of the classical symbiotic star YY Her in 1993 and photoelectric UBV observations of the star’s eclipse in 1997. The duration of the phase of lowest brightness, when the U brightness had decreased by ~1.3m, was ~0.17 P orb (P orb is the orbital period). If this phase is due to the total eclipse of ~70% of the radiation of the circumstellar envelope, this duration implies that the cool component of YY Her fills its Roche lobe, the bulk of the envelope’s volume emission measure is concentrated around the hot component in a region with rather sharp boundaries r R giant (R giant is the giant’s radius), and the line of sight is close to the binary orbital plane. We model fit the spectral energy distribution of YY Her to obtain estimates of the parameters of several structural components of the system. The red giant’s spectral type correlates with its visual brightness and does not correlate with the hot component’s brightness. At minimum brightness, the hot component’s luminosity fluctuates about that of its cool companion (L h, bol /L c, bol ≈0.9), and its temperature is T h ≈(9–11)×104 K. Activity of the hot component of YY Her is accompanied by increased brightness and reduced temperature (L h, bol T h ?5 ), though the relation between these parameters is not unique. At maximum brightness, L h, bol /L c, bol ≈10 and T h ≈6.0×104 K. If the red giant fills its Roche lobe, the hot component’s luminosity is ~3.3 × 104 L . The active period of YY Her lasted about 5 years, and the activity decrease was not monotonic.  相似文献   

12.
57Fe Mössbauer spectra are presented for synthetic cation-deficient Fe2TiO4 and FeCr2O4 spinel particles (<1μm) at various temperatures. The spectra of ferrimagnetic cation-deficient Fe2TiO4 show characteristic features due to relaxation because of superparamagnetism and spin relaxation in the temperature range 5–294 K. At 5 K and 78 K, a superposition of at least two sextets is observed which appear to arise from Fe3+ onA-sites (Fe A 3+ andB-sites (Fe B 3+ ) of the spinal lattice with magnetic hyperfine fields at 5 K ofB hf ((Fe B 3+ )≈47.5 T andB hf (Fe B 3+ )≈51.0 T, respectively. Cation-deficient FeCr2O4 particles reveal at 78 K a fieldB hf (Fe3+)≈46.9 T and exhibit relaxation spectra as a consequence of superparamagnetism in the temperature range 80 K - ~300 K. At 294 K, quadrupole splitting Δ(Fe A 3+ )=0.92 mm/s and isomer shift δ(Fe A 3+ )=0.29 mm/s (relative to metallic Fe) are measured. For both compounds the magnetic hyperfine fieldsB hf are discussed in terms of supertransferred hyperfine fields involving vacancies and in the case of cation-deficient Fe2TiO4 also diamagnetic Ti4+ neighbours of the Fe ions.  相似文献   

13.
Electron paramagnetic resonance (EPR) measurements of natural anhydrite CaSO4, celestite SrSO4 and barite BaSO4 have revealed the presence of PO 3 2? and SO 3 ? radicals. Hyperfine structure from33S has been detected and measured for the first time. Low-symmetry effects, which are manifested in noncoincidence of g and hyperfine axes, were observed for SO 3 ? . The dynamics of one of the two SO 3 ? types in anhydrite has been investigated. Variations of spin Hamiltonian parameters with temperature have been attributed to thermally induced jumps between the two magnetically inequivalent sites of this center.  相似文献   

14.
The results of X-ray fluorescence Ka 1,2 and Kβ1,β′-spectra of iron in 54 samples, including 23 minerals, are presented. Spectrum characteristics are mainly dependent on the environment of iron in the sample, the most susceptible parameter being the chemical shift δβ1. For the compounds investigated δβ1 varies between ?1.58 eV and +1.56 eV when referring to metallic iron. Chemical shifts of compounds with predominantly covalent bonds exhibit more negative values, compounds with metallic bonds nearly vanishing values and compounds with predominantly ionic bonds more positive values. The FeKβ1,β′-group of lines is actually a superposition of three lines: the long-wave line β′ and two overlapping lines β 1 5 and β 1 7 of which the superposition is conventionally denoted as β1. The relative intensity of β 1 5 increases with ionicity of the bond, while that of β 1 7 decreases. The effective charge of iron has been determined for a group of iron-bearing minerals.  相似文献   

15.
Molecular orbital calculations are presented for the copper-sulfur polyhedral clusters CuS 4 7? , CuS 4 6? , CuS 3 5? and CuS 3 4? , which occur in many minerals. Calculated and experimental optical and X-ray energies are found to be in good agreement. The crystal field orbitals of Cu+ in tetrahedrally coordinated sulfides are found to be less tightly bound than the S3p nonbonding orbitals by about 2–3 eV whereas the e and t 2 crystal field orbitals are split by about 1 eV. The crystal field splitting of Cu2+ in tetrahedral coordination is about 0.7–0.8 eV while the separation of the S3p nonbonding orbitals and the partially filled t 2 crystal field orbital is about 2 eV. In triangular coordination both the Cu+ and Cu2+ crystal field orbitals are more stable than in tetrahedral coordination, more widely split and more strongly mixed with the S3p orbitals. CuS is shown to be unstable as the mixed oxidation state compound Cu2+III (Cu+IV)2S2?(S 2 2? ); rather each Cu is predicted to have a fractional oxidation state and partially-empty crystal field orbitals.  相似文献   

16.
Groundwater, surface water, soil and river sediment samples, and information on land use in the Nanfei River basin (NRB) of China have been analyzed to study the geochemistry, distribution, and mobilization of phosphorus. The distribution of phosphate (PO 4 3??/sup> ) and the relationships between PO 4 3??/sup> and several constituents in groundwater were studied. Partial correlation analysis relating PO 4 3??/sup> to types of land use was conducted using the data analyzing tool SPSS 15.0. The processes controlling the transport of PO 4 3??/sup> are discussed. The conclusions from this study are: (1) urban land use has obvious impact on PO 4 3??/sup> in groundwater, the average concentration of PO 4 3??/sup> being 4.37?mg/L, greater than that resulting from farmland and mixed land use, which have average PO 4 3??/sup> concentrations of 0.10 and 0.18?mg/L, respectively; (2) the partial correlation between PO 4 3??/sup> and types of land use is significant with a coefficient of 0.760; (3) the PO 4 3??/sup> concentrations in surface water are generally higher than those in groundwater, and the total phosphorus (TP) concentrations in river sediments are generally higher than those in soil samples; (4) groundwater is a carrier of PO 4 3??/sup> and is likely responsible for the redistribution of PO 4 3??/sup> in different regions of NRB.  相似文献   

17.
Given the direction cosines a i = (a 1 i , a 2 i , a 3 i )corresponding to a set of pspherically projected fabric poles, an initial estimate x′ = (x1, x2, x3, x4)for the angular radius x4,and direction cosines of the center of the least-squares small circle which minimizes the sum of the squares of the angular residuals $$r = \sum\limits_p {\left[ {x_4 - \cos ^{ - 1} \left( {a_1^i x_1 + a_2^i x_2 + a_3^i x_3 } \right)} \right]} ^2 $$ can be iteratively improved by taking xj+1 = xj + Δxwhere xj is the value of xat the jth iteration and $$\Delta x = - H_j^{ - 1} \left[ {q_j + x_j \left( {x'_j H_j^{ - 1} x_j } \right)\left( {q_j - x'_j H_j^{ - 1} q_j } \right)} \right],$$ where As an initial approximation for xwe have found it convenient to ignore the fact that the data are constrained to lie on the surface of the reference sphere and to use the parameters of a least-squares plane through the given poles. Generalization of this approach to fitting variously constrained great and small circles is easily made. The relative merits of differently constrained fits to the same data can be tested approximately if it is assumed that the errors in the location of the poles are isotropic and normally distributed. It is thus possible to statistically assess the relative significance of conflicting structural models which predict different geometrical patterns of fabric elements.  相似文献   

18.
The methods used by earlier workers for evaluating material balance in core-mantle-matrix type differentiated systems are examined in detail. It is demonstrated that these methods can be successfully employed only when the true core-mantle volume ratio is known. On geometric grounds, it is rarely possible to have a reliable estimate of this ratio from natural specimen. Consequently, the scope of balance evaluation by these methods is severely restricted. From theoretical consideration of mass transfer relations in differentiated systems, a new computational method is proposed that can be effectively employed for quantitative balance evaluation without any prior knowledge of the core-mantle volume ratio provided the chemical analyses of the core, mantle and matrix are available. This method involves the application of the following mass balance equation: $$m_1 x_1^i + m_2 x_2^i = m_0 x_0^i {\text{ (}}i = {\text{1,2}}...{\text{,}}n{\text{)}}$$ where m 1 and m 2 are the mass of the core and mantle respectively, m 0 is the mass of the matrix involved in differentiation, and x 1 i , x 2 i , x 0 i are the weight fractions of the component i in the core, mantle and matrix respectively. This method would also permit a quantitative estimation of the materials added to or removed from the system. Three differentiated systems previously investigated by Mehnert (1951, 1968), Loberg (1963) and Kretz (1966) are selected for balance evaluation by the proposed method and the results are compared with the published balance analyses.  相似文献   

19.
Laihuite reported in the present paper is a new iron silicate mineral found in China with the following characteristics:
  1. This mineral occurs in a metamorphic iron deposit, associated with fayalite, hypersthene, quartz, magnetitc, etc.
  2. The mineral is opaque, black in colour, thickly tabular in shape with luster metallic to sub-metallic, two perfect cleavages and specific gravity of 3.92.
  3. Its main chemical components are Fe and Si with Fe3+>Fe2+. The analysis gave the formula of Fe Fe 1.00 3+ ·Fe 0.58 2+ ·Mg 0.03 2+ ·Si0.96O4.
  4. Its DTA curve shows an exothermic peak at 713°C.
  5. The mineral has its own infrared spectrum distinctive from that of other minerals.
  6. This mineral is of orthorhombic system; space group:C 2h /5 ?P21/c; unit cell:α=5.813ű0.005,b=4.812ű0.005,c=10.211ű0.005,β=90.87°.
  7. The Mössbauer spectrum of this mineral is given, too.
  相似文献   

20.
In 61 pairs of coexisting biotites and muscovites from the Central Alps total Al scatters considerably, but in both series a gradual increase is noticed with increasing metamorphic grade. The ratio Al Mu tot /Al Bi tot remains virtually constant (1.61 average for greenschist facies, 1.57 for amphibolite facies). Tetrahedral Al varies little in biotites and increases in muscovites-phengites with rising metamorphic grade; accordingly the ratio Al Mu IV /Al Bi IV increases slightly with grade. Far the best control of metamorphism is evidenced by octahedral Al. In the muscovite series, and still more pronounced in the biotite series, AlVI increases with increasing metamorphic grade. Consequently 1 $$K_D = \frac{{Al_{Mu}^{VI} }}{{Al_{Bl}^{VI} }}$$ decreases from 14 to 3. A map (Fig. 6) representing the regional distribution of the KD values locates a 100 km long and 23 km broad central zone with low KD. The outline of this central core almost coincides with the isograds anorthite-diopside-calcite and labradorite-pyroxene-hornblende of the Tertiary regional metamorphism; with some deviations this core also agrees with the zone in which phenomena of partial anatexis are observed. The KD values of micas from anateotic pegmatites agree with those of associated gneisses and schists. The study demonstrates that in the course of progressive regional metamorphism equilibrium has been approached to an unexpected extent and that the two micas coexisted in a strict sense.  相似文献   

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