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1.
Martin Kunz George A. Lager Hans-Beat Bürgi Maria Teresa Fernandez-Diaz 《Physics and Chemistry of Minerals》2006,33(1):17-27
The H-atom environment in a Tilly Foster chondrodite was analyzed using single-crystal neutron-diffraction data collected at 500, 700 and 900 K and previously published low temperature data collected at 10, 100 and 300 K on the same crystal (Mg4.64Fe0.28Mn0.014Ti0.023(Si1.01O4)2F1.16(OH)0.84; Friedrich et al. in Am Mineral 86:981–989, 2001). The full mean square displacement matrix Σ of the O–H pair was determined from the temperature dependence of the anisotropic displacement parameters, enabling a proper correction of the O–H bond for thermal vibration without assumptions about the correlation of O and H movements. The results show that the perpendicular O–H motions in chondrodite are intermediate between the riding and the independent motion models. The corrected O–H bond lengths do not change with temperature whereas the corrected H···F distances show an increase of ~0.02 Å with temperature, as do the Mg–O distances. This result shows that spectroscopic observations on the strength of the covalent O–H bond cannot be interpreted unambiguously in terms of a corresponding behaviour of the associated H···O/F hydrogen bond. 相似文献
2.
Esther S. Posner Przemyslaw Dera Robert T. Downs John D. Lazarz Peyton Irmen 《Physics and Chemistry of Minerals》2014,41(9):695-707
The crystal structures of natural jadeite, NaAlSi2O6, and synthetic kosmochlor, NaCrSi2O6, were studied at room temperature, under hydrostatic conditions, up to pressures of 30.4 (1) and 40.2 (1) GPa, respectively, using single-crystal synchrotron X-ray diffraction. Pressure–volume data have been fit to a third-order Birch–Murnaghan equation of state yielding V 0 = 402.5 (4) Å3, K 0 = 136 (3) GPa, and K 0 ′ = 3.3 (2) for jadeite and V 0 = 420.0 (3) Å3, K 0 = 123 (2) GPa and K 0 ′ = 3.61 (9) for kosmochlor. Both phases exhibit anisotropic compression with unit-strain axial ratios of 1.00:1.95:2.09 for jadeite at 30.4 (1) GPa and 1:00:2.15:2.43 for kosmochlor at 40.2 (1) GPa. Analysis of procrystal electron density distribution shows that the coordination of Na changes from 6 to 8 between 9.28 (Origlieri et al. in Am Mineral 88:1025–1032, 2003) and 18.5 (1) GPa in kosmochlor, which is also marked by a decrease in unit-strain anisotropy. Na in jadeite remains six-coordinated at 21.5 (1) GPa. Structure refinements indicate a change in the compression mechanism of kosmochlor at about 31 GPa in both the kinking of SiO4 tetrahedral chains and rate of tetrahedral compression. Below 31 GPa, the O3–O3–O3 chain extension angle and Si tetrahedral volume in kosmochlor decrease linearly with pressure, whereas above 31 GPa the kinking ceases and the rate of Si tetrahedral compression increases by greater than a factor of two. No evidence of phase transitions was observed over the studied pressure ranges. 相似文献
3.
The effects of low-temperature on the crystal structure of a natural epidote [Ca1.925Fe0.745Al2.265Ti0.004Si3.037O12(OH), a = 8.8924(7), b = 5.6214(3), c = 10.1547(6)? and β = 115.396(8)° at room conditions, Sp. Gr. P21
/m] have been investigated with a series of structure refinements down to 100 K on the basis of X-ray single-crystal diffraction
data. The reflection conditions confirm that the space group is maintained within the T-range investigated. Structural refinements at all temperatures show the presence of Fe3+ at the octahedral M(3) site only [%Fe(M3) = 70.6(4)% at 295 K]. Only one independent proton site was located and two possible
H-bonds occur, with O(10) as donor and O(4) and O(2) as acceptors. The H-bonding scheme is maintained down to 100 K and is
supported by single crystal room-T polarised FTIR data. FTIR Spectra over the region 4,000–2,500 cm−1 are dominated by the presence of a strongly pleochroic absorption feature which can be assigned to protonation of O(10)–O(4).
Previously unobserved splitting of this absorption features is consistent with a NNN influence due to the presence of Al and
Fe3+ on the nearby M(3) site. An additional relatively minor absorption feature in FTIR spectra can be tentatively assigned to
protonation of O(10)–O(2). Low-T does not affect significantly the tetrahedral and octahedral bond distances and angles, even when distances are corrected
for “rigid body motions”. A more significant effect is observed for the bond distances of the distorted Ca(1)- and Ca(2)-polyhedra,
especially when corrected for “non-correlated motion”. The main low-T effect is observed on the vibrational regime of the atomic sites, and in particular for the two Ca-sites. A significant reduction
of the magnitude of the thermal displacement ellipsoids, with a variation of U
eq
(defined as one-third of the trace of the orthogonalised U
ij
tensor) by ~40% is observed for the Ca-sites between 295 and 100 K. Within the same T-range, the U
eq
of the octahedral and oxygen sites decrease similarly by ~35%, whereas those of the tetrahedral cations by ~22%. 相似文献
4.
《Comptes Rendus Geoscience》2019,351(2-3):121-128
We present a synchrotron-based, single-crystal X-ray diffraction and Raman spectroscopy study of natural green dioptase (Cu6Si6O18·6H2O) up to ∼30 GPa at room temperature. The lattice parameters of dioptase exhibit continuous compression behavior up to ∼14.5 GPa, whereupon a structural transition is observed. Pressure–volume data below 14.5 GPa were fitted to a second-order Birch–Murnaghan equation of state with V0 = 1440(2) Å3 and K0 = 107(2) GPa, with K0′ = 4(fixed). The low-pressure form of dioptase exhibits anisotropic compression with axial compressibility βa > βc in a ratio of 1.14:1.00. Based on the diffraction data and Raman spectroscopy, the new high-pressure phase could be regarded as a dehydrated form of dioptase in the same symmetry group. Pressure-induced dehydration of dioptase contributes broadly to our understanding of the high-pressure crystal chemistry of hydrous silicates containing molecular water groups. 相似文献
5.
Fernando Cámara G. Diego Gatta Martin Meven Daria Pasqual 《Physics and Chemistry of Minerals》2012,39(1):27-45
The thermo-elastic behaviour and the temperature-induced structure evolution of a natural Fe-free zoisite have been investigated
by in situ single-crystal X-ray and neutron diffraction. Neither discontinuities in volume expansion nor changes in symmetry
have been observed up to 1,023 K. Zoisite shows a negative thermal expansion along [100] at T > 700 K, while a continuous positive expansion occurs on the (100) plane. Two different regimes in the anisotropic thermal
behaviour of zoisite can be distinguished (i.e. at T < 700 K and T > 700 K), corresponding to an increase in the volumetric thermal expansion at T > 700 K. The structure evolution with temperature has been described by a series of X-ray and neutron refinements at different
temperatures. In particular, the M(3) polyhedra show a significant octahedral flattening and expansion in the equatorial plane
with T. All [SiO4] tetrahedra show a regularization with increasing T. The neutron refinements show no change in the configuration of the hydrogen bonding at least up to 873 K. The effects of
the T-induced main deformation mechanisms on the anisotropic elastic behaviour of zoisite are discussed. A comparison with the
thermal behaviour of epidote has been carried out. 相似文献
6.
Yusheng Zhao David Schiferl Thomas J. Shankland 《Physics and Chemistry of Minerals》1995,22(6):393-398
P-V-T data of MgSiO3 orthoenstatite have been measured by single-crystal X-ray diffraction at simultaneous high pressures (in excess of 4.5 GPa) and temperatures (up to 1000 K). The new P-V-T data of the orthoenstatite, together with previous compression data and thermal expansion data, are described by a modified Birch-Murnaghan equation of state for diverse temperatures. The fitted thermoelastic parameters for MgSiO3 orthoenstatite are: thermal expansion ?α/?P with values of a=2.86(29)×10-5 K-1 and b=0.72(16)×10-8 K-2; isothermal bulk modulus K T o =102.8(2) GPa; pressure derivative of bulk modulus K′=?K/?P=10.2(1.2); and temperature derivative of bulk modulus K=?K/?T=-0.037(5) GPa/K. The derived thermal Grüneisen parameter is γ th=1.05 for ambient conditions; Anderson-Grüneisen parameter is δ T o =11.6, and the pressure derivative of thermal expansion is ?α/?P=-3.5×10-6K-1 GPa-1. From the P-V-T data and the thermoelastic equation of state, thermal expansions at two constant pressures of 1.5 GPa and 4.0 GPa are calculated. The resulting pressure dependence of thermal expansion is Δα/ΔP=-3.2(1)× 10-6 K-1 GPa-1. The significantly large values of K′, K, δ T and ?α/?P indicate that compression/expansion of MgSiO3 orthoenstatite is very sensitive to changes of pressure and temperature. 相似文献
7.
G. Diego Gatta Ilaria Adamo Martin Meven Erica Lambruschi 《Physics and Chemistry of Minerals》2012,39(10):829-840
The chemical composition and the crystal structure of pezzottaite [ideal composition Cs(Be2Li)Al2Si6O18; space group: ${\it{R}} \overline{\text{3}} $ c, a?=?15.9615(6) ?, c?=?27.8568(9) ?] from the type locality in Ambatovita (central Madagascar) were investigated by electron microprobe analysis in wavelength dispersive mode, thermo-gravimetric analysis, Fourier-transform infrared spectroscopy, single-crystal X-ray (at 298?K) and neutron (at 2.3?K) diffraction. The average chemical formula of the sample of pezzottaite resulted Cs1,Cs2(Cs0.565Rb0.027K0.017)Σ0.600 Na1,Na2(Na0.101Ca0.024)Σ0.125Be2.078Li0.922 Al1,Al2(Mg0.002Mn0.002Fe0.003Al1.978)Σ1.985 Si1,Si2,Si3(Al0.056Si5.944)Σ6O18·0.27H2O. The (unpolarized) IR spectrum over the region 3,800–600?cm?1 was collected and a comparison with the absorption bands found in beryl carried out. In particular, two-weak absorption bands ascribable to the fundamental H2O stretching vibrations (i.e. 3,591 and 3,545?cm?1) were observed, despite the mineral being nominally anhydrous. The X-ray and neutron structure refinements showed: (a) a non-significant presence of aluminium, beryllium or lithium at the Si1, Si2 and Si3 sites, (b) the absence (at a significant level) of lithium at the octahedral Al1, Al2 and Al3 sites and (c) a partial lithium/beryllium disordering between tetrahedral Be and Li sites. 相似文献
8.
9.
Antigorite equation of state and anomalous softening at 6 GPa: an in situ single-crystal X-ray diffraction study 总被引:1,自引:0,他引:1
Fabrizio Nestola Ross J. Angel Jing Zhao Carlos J. Garrido Vicente López Sánchez-Vizcaíno Giancarlo Capitani Marcello Mellini 《Contributions to Mineralogy and Petrology》2010,160(1):33-43
The compressibility of antigorite has been determined up to 8.826(8) GPa, for the first time by single crystal X-ray diffraction in a diamond anvil cell, on a specimen from Cerro del Almirez. Fifteen pressure–volume data, up to 5.910(6) GPa, have been fit by a third-order Birch–Murnaghan equation of state, yielding V 0 = 2,914.07(23) Å3, K T0 = 62.9(4) GPa, with K′ = 6.1(2). The compression of antigorite is very anisotropic with axial compressibilities in the ratio 1.11:1.00:3.22 along a, b and c, respectively. The new equation of state leads to an estimation of the upper stability limit of antigorite that is intermediate with respect to existing values, and in better agreement with experiments. At pressures in excess of 6 GPa antigorite displays a significant volume softening that may be relevant for very cold subducting slabs. 相似文献
10.
R. Miletich M. Nowak F. Seifert R. J. Angel G. Brandstätter 《Physics and Chemistry of Minerals》1999,26(6):446-459
The high-pressure behaviour of chromous orthosilicate, Cr2SiO4, has been studied by means of single-crystal X-ray diffraction and electronic absorption spectroscopy. X-ray diffraction data show that the structure remains orthorhombic to the highest pressure reached of 9.22?GPa. The compressibility of the unit-cell is strongly anisotropic with the c axis approximately six times more compressible than the a and b axes. A third-order Birch-Murnaghan equation of state fitted to the volume-pressure data yields V 0?=?610.10(3)?Å3, K = 94.7(4)?GPa, K′?=?8.32(14). Cr2SiO4 is therefore more compressible than the isostructural Cd analogue, even though its molar volume is smaller. This unusual behaviour can be attributed to the fact that the Cr atom is too small for the six-coordinated site that it occupies, and the site is therefore strongly distorted. Structure refinements indicate that under high pressures the Cr atom remains strongly displaced from the central position of the octahedron. Polarized and unpolarized electronic absorption spectra include a strong absorption band occuring at 18.300 cm?1 for E//c (which is parallel to the shortest Cr-Cr vector in the structure) which has an unusually large half width (5000?cm?1), indicative of electronic interaction between metal centres. Deconvolution of unpolarized high-pressure spectra show that the relative integrated intensity of this component increases linearly from 40% at 1?bar to 60% at 11.2?GPa. Both the structural changes and the absorption spectra at high pressures suggest that pairs of adjacent Cr atoms in chromous orthosilicate form chromium dimers with a weak metal-metal bond, which is consistent with the diamagnetic response found at ambient pressure. 相似文献
11.
12.
D. Gournis A. Lappas M. A. Karakassides D. Többens A. Moukarika 《Physics and Chemistry of Minerals》2008,35(1):49-58
Neutron powder diffraction measurements on lithium and cesium saturated montmorillonite samples before and after heat treatment
at 300°C are studied, in order to undertake a complete refinement of crystal structure and unravel the migration mechanism
for the interlayer cations of Li or Cs. Rietveld analysis of the corresponding diffraction patterns finds that montmorillonite
crystallizes in the C2/m space group with unit cell dimensions consistent with the size of the specific interlayer cation. We show that thermal treatment
affects the two types of samples in a different way. This is with respect to their unit cell dimensions and the migration
of Li from the 2b to the 2c clay lattice site, in constrast to the Cs positioning which remains effectively unchanged. 相似文献
13.
Hongwu Xu Yusheng Zhao Donald D. Hickmott Nina J. Lane Sven C. Vogel Jianzhong Zhang Luke L. Daemen 《Physics and Chemistry of Minerals》2013,40(10):799-810
To study the structural behavior of brucite at high temperature, we conducted in situ neutron diffraction experiments of a deuterated brucite powder sample, Mg(OD)2, in the temperature range 313–583 K. The sample was stable up to 553 K, above which it started to decompose into periclase (MgO) and D2O vapor. Rietveld analyses of the obtained data were performed using both single-site and three-site split-atom hydrogen models. Our results show that with increasing temperature, unit-cell parameter c increases at a rate ~7.7 times more rapidly than a. This large anisotropy of thermal expansion is primarily due to rapid increase in the interlayer thickness along the c-axis on heating. The amplitudes of thermal vibration for Mg, O, and D increase linearly with increasing temperature; however, the rate of the increase for the lighter D is much larger. In addition, D vibrates anisotropically with a higher magnitude within the (001) plane, as confirmed by our first-principles phonon calculations. On heating, the interatomic distances between a given D and its associated O and D from the adjacent [MgO6] layer increase, whereas the O–D bond length decreases. This behavior suggests weakened D···O and D···D interlayer interactions but strengthened O–D bonding with increasing temperature. 相似文献
14.
The paper compares pole figure determinations with neutron diffraction and X-ray diffraction on experimentally deformed carbonate rocks, a coarse grained marble and fine grained limestone. Neutron diffraction enables determination of complete pole figures on a single spherical specimen and is advantageous for coarse grained materials. Results obtained with both diffraction techniques agree satisfactorily, although uncertainties introduced by counting statistics are more serious for neutrons than for X-rays. Continuous detectors add new possibilities which are still little explored. 相似文献
15.
S. Carbonin F. Martignago G. Menegazzo A. Dal Negro 《Physics and Chemistry of Minerals》2002,29(8):503-514
Two MgAl2O4 stoichiometric spinel crystals, one natural and one synthetic, were heated from 25 to 950 °C and studied in situ by single-crystal
X-ray diffraction. The natural crystal, quenched from 850 °C, was further heated and cooled. Thermal expansion was characterized,
and cation partitioning at the various temperatures was determined according to a model purposely constructed for high-temperature
bond lengths. It was found that the structural evolution of the samples with temperature depended on order–disorder at room
temperature. At the temperatures lower than the beginning of cation exchange, thermal expansion was completely reversible
and the oxygen coordinate remained stable in spite of varying temperatures. At the temperature at which cation exchange starts,
the disordered samples first tend to order and then to disorder at higher temperatures, at variance with the ordered sample,
which tends to disorder steadily. In general, the evolution of the spinel structural state on cooling and heating over the
same temperature range and the same time intervals does not follow the same path. In particular, in the 600–950 °C range,
only partially reversible order–disorder processes occurred in the time span used for the experiments.
Received: 16 July 2001 / Accepted: 8 January 2002 相似文献
16.
用X射线衍射分析的方法测定了12个田黄样品,其中,青田石1个,寿山石9个,昌化田黄石2个。确定青田石由叶蜡石(58%)、绢云母(36.1%)和高岭石(5.9%)组成;昌化田黄石由迪开石组成;寿山石分别由迪开石、高岭石、叶蜡石及绢云母组成。 相似文献
17.
Ryosuke Sinmyo Elena Bykova Catherine McCammon Ilya Kupenko Vasily Potapkin Leonid Dubrovinsky 《Physics and Chemistry of Minerals》2014,41(6):409-417
Magnesium silicate perovskite is the predominant phase in the Earth’s lower mantle, and it is well known that incorporation of iron has a strong effect on its crystal structure and physical properties. To constrain the crystal chemistry of (Mg, Fe)SiO3 perovskite more accurately, we synthesized single crystals of Mg0.946(17)Fe0.056(12)Si0.997(16)O3 perovskite at 26 GPa and 2,073 K using a multianvil press and investigated its crystal structure, oxidation state and iron-site occupancy using single-crystal X-ray diffraction and energy-domain Synchrotron Mössbauer Source spectroscopy. Single-crystal refinements indicate that all iron (Fe2+ and Fe3+) substitutes on the A-site only, where \( {\text{Fe}}^{ 3+ } /\Upsigma {\text{Fe}}\sim 20\,\% \) based on Mössbauer spectroscopy. Charge balance likely occurs through a small number of cation vacancies on either the A- or the B-site. The octahedral tilt angle (Φ) calculated for our sample from the refined atomic coordinates is 20.3°, which is 2° higher than the value calculated from the unit-cell parameters (a = 4.7877 Å, b = 4.9480 Å, c = 6.915 Å) which assumes undistorted octahedra. A compilation of all available single-crystal data (atomic coordinates) for (Mg, Fe)(Si, Al)O3 perovskite from the literature shows a smooth increase of Φ with composition that is independent of the nature of cation substitution (e.g., \( {\text{Mg}}^{ 2+ } - {\text{Fe}}^{ 2+ } \) or \( {\text{Mg}}^{ 2+ } {\text{Si}}^{ 4+ } - {\text{Fe}}^{ 3+ } {\text{Al}}^{ 3+ } \) substitution mechanism), contrary to previous observations based on unit-cell parameter calculations. 相似文献
18.
Kevin S. Knight William G. Marshall Philip M. Hawkins 《Physics and Chemistry of Minerals》2014,41(6):461-472
The fluoroperovskite phase RbCaF3 has been investigated using high-pressure neutron powder diffraction in the pressure range ~0–7.9 GPa at room temperature. It has been found to undergo a first-order high-pressure structural phase transition at ~2.8 GPa from the cubic aristotype phase to a hettotype phase in the tetragonal space group I4/mcm. This transition, which also occurs at ~200 K at ambient pressure, is characterised by a linear phase boundary and a Clapeyron slope of 2.96 × 10?5 GPa K?1, which is in excellent agreement with earlier, low-pressure EPR investigations. The bulk modulus of the high-pressure phase (49.1 GPa) is very close to that determined for the low-pressure phase (50.0 GPa), and both are comparable with those determined for the aristotype phases of CsCdF3, TlCdF3, RbCdF3, and KCaF3. The evolution of the order parameter with pressure is consistent with recent modifications to Landau theory and, in conjunction with polynomial approximations to the pressure dependence of the lattice parameters, permits the pressure variation of the bond lengths and angles to be predicted. On entering the high-pressure phase, the Rb–F bond lengths decrease from their extrapolated values based on a third-order Birch–Murnaghan fit to the aristotype equation of state. By contrast, the Ca–F bond lengths behave atypically by exhibiting an increase from their extrapolated magnitudes, resulting in the volume and the effective bulk modulus of the CaF6 octahedron being larger than the cubic phase. The bulk moduli for the two component polyhedra in the tetragonal phase are comparable with those determined for the constituent binary fluorides, RbF and CaF2. 相似文献
19.
D. W. Fan M. N. Ma W. G. Zhou S. Y. Wei Z. Q. Chen H. S. Xie 《Physics and Chemistry of Minerals》2011,38(2):95-99
The high-pressure X-ray diffraction study of a natural arsenopyrite was investigated up to 28.2 GPa using in situ angle-dispersive
X-ray diffraction and a diamond anvil cell at National Synchrotron Light Source, Brookhaven National Laboratory. The 16:3:1
methanol–ethanol–water mixture was used as a pressure-transmitting medium. Pressures were measured using the ruby-fluorescence
method. No phase change has been observed up to 28.2 GPa. The isothermal equation of state (EOS) was determined. The values
of K
0, and K′
0 refined with a third-order Birch–Murnaghan EOS are K
0 = 123(9) GPa, and K′
0 = 5.2(8). Furthermore, we confirm that the linear compressibilities (β) along a, b and c directions of arsenopyrite is elastically isotropic (β
a
= 6.82 × 10−4, β
b
= 6.17 × 10−4 and β
c
= 6.57 × 10−4 GPa−1). 相似文献
20.
M. Zhang H.-W. Meyer L. A. Groat U. Bismayer E. K. H. Salje G. Adiwidjaja 《Physics and Chemistry of Minerals》1999,26(7):546-553
Powder infrared spectroscopy and X-ray diffraction techniques on single crystals were used to study the thermal behaviour
of malayaite, CaSnSiO5. Infrared spectra show a discontinuity in the temperature evolution of phonon frequencies and absorbance near 500 K. However,
crystal structure data collected at 300, 450, 550, 670, and 750 K show no evidence of a symmetry-breaking phase transition
and no split positions. The most obvious change with heating is a tumbling motion of the SnO6 octahedra and an increase of the anisotropic displacement factors of Ca. The thermal evolution of the mean-square vibrational
amplitude of the Ca atom shows a pronounced change in slope near 500 K. The evidence suggests that the 500 K anomaly in malayaite
is more similar in character to the 825 K (β-γ) transition as opposed to the 496 K (α-β) transition in synthetic titanite.
Received: 26 March 1998 / Revised, accepted: 23 December 1998 相似文献