Ab initio quantum mechanical study of γ-AlOOH boehmite: structure and vibrational spectrum     

Yves Noel  Raffaella Demichelis  Fabien Pascale  Piero Ugliengo  Roberto Orlando  Roberto Dovesi 《Physics and Chemistry of Minerals》2009,36(1):47-59

The structure and vibrational spectrum of boehmite have been investigated at the quantum-mechanical level with the CRYSTAL code, using a Gaussian-type basis set and the B3LYP Hamiltonian. Three space groups are considered in this study: Cmcm, Cmc2₁, P2₁/c. Cmcm turns out to correspond to a transition state, whereas Cmc2₁ and P2₁/c are minimum energy structures. The difference among them is the position of H atoms only, the Al-O frame being essentially the same. Harmonic frequencies at the Γ point have been computed. The comparison between calculated and experimental frequencies shows a good agreement for the Al-O part of the spectrum (under 790 cm⁻¹). For the Al-OH bending modes (800–1,300 cm⁻¹) an absolute differences of 50–100 cm⁻¹ is observed; for the OH stretching modes (3,200–3,500 cm⁻¹) it increases to 120–200 cm⁻¹: anharmonicity is large because OH groups are involved in strong hydrogen bonds.  相似文献   

High-pressure phase transition and behavior of protons in brucite Mg(OH)2: a high-pressure–temperature study using IR synchrotron radiation     

K. Shinoda  M. Yamakata  T. Nanba  H. Kimura  T. Moriwaki  Y. Kondo  T. Kawamoto  N. Niimi  N. Miyoshi  N. Aikawa 《Physics and Chemistry of Minerals》2002,29(6):396-402

 Infrared absorption spectra of brucite Mg (OH)₂ were measured under high pressure and high temperature from 0.1 MPa 25 °C to 16 GPa 360 °C using infrared synchrotron radiation at BL43IR of Spring-8 and a high-temperature diamond-anvil cell. Brucite originally has an absorption peak at 3700 cm⁻¹, which is due to the OH dipole at ambient pressure. Over 3 GPa, brucite shows a pressure-induced absorption peak at 3650 cm⁻¹. The pressure-induced peak can be assigned to a new OH dipole under pressure. The new peak indicates that brucite has a new proton site under pressure and undergoes a high-pressure phase transition. From observations of the pressure-induced peak under various P–T condition, a stable region of the high-pressure phase was determined. The original peak shifts to lower wavenumber at −0.25 cm⁻¹ GPa⁻¹, while the pressure-induced peak shifts at −5.1 cm⁻¹ GPa⁻¹. These negative dependences of original and pressure-induced peak shifts against pressure result from enhanced hydrogen bond by shortened O–H···O distance, and the two dependences must result from the differences of hydrogen bond types of the original and pressure-induced peaks, most likely from trifurcated and bent types, respectively. Under high pressure and high temperature, the pressure-induced peak disappears, but a broad absorption band between 3300 and 3500 cm⁻¹ was observed. The broad absorption band may suggest free proton, and the possibility of proton conduction in brucite under high pressure and temperature. Received: 16 July 2001 / Accepted: 25 December 2001  相似文献   

The influence of pressure on the structure and dynamics of hydrogen bonds in zoisite and clinozoisite     

Björn Winkler  Julian D. Gale  Keith Refson  Dan J. Wilson  Victor Milman 《Physics and Chemistry of Minerals》2008,35(1):25-35

Density functional theory calculations have been used to study the pressure-induced changes of the hydrogen bond of Fe-free orthozoisite and clinozoisite and the concomitant shifts of the OH-stretching frequencies. Two independent parameter-free lattice dynamical calculations have been employed. One was based on a plane-wave basis set in conjunction with norm-conserving pseudopotentials and a density functional perturbation theory approach, while the other used a localised basis set and a finite displacement algorithm for the lattice dynamical calculations. Both models confirm the unusually large pressure-induced red-shift found experimentally (−33.89 cm⁻¹/GPa) in orthozoisite, while the pressure-induced shifts in clinozoisite are much smaller (−5 to −9 cm⁻¹/GPa). The atomistic model calculations show that in orthozoisite the nearly linear O–H⋯O arrangement is compressed by about 8% on a pressure increase to 10 GPa, while concomitantly the O–H distance is significantly elongated (by 2.5% at 10 GPa). In clinozoisite, the O–H⋯O arrangement is kinked at ambient conditions and remains kinked at high pressures, while the O-H distance is elongated by only 0.5% at 10 GPa. The current calculations confirm that correlations between the distances and dynamics of hydrogen bonds, which have been established at ambient conditions, cannot be used to infer hydrogen positions at high pressures.  相似文献   

Variation of infrared absorption spectra in the system Bi2Al4−x Fe x O9 (x = 0–4), structurally related to mullite     

D. Voll  A. Beran  H. Schneider 《Physics and Chemistry of Minerals》2006,33(8-9):623-628

The crystal structure of Bi₂Al_4−x Fe _x O₉ compounds (x = 0–4) has striking similarities with the crystal structure of mullite. A complete substitution of Al by Fe³⁺ in both octahedral and tetrahedral sites is a particular structural feature. The infrared (IR) spectra of the Bi₂M₄O₉ compounds (M = Al, Fe³⁺) are characterised by three band groups with band maxima in the 900–800, 800–600 and 600–400 cm⁻¹ region. Based on the spectroscopic results obtained from mullite-type phases, the present study focuses on the composition-dependent analysis of the 900–800 cm⁻¹ band group, which is assigned to Al(Fe³⁺)–O stretching vibrations of the corner-sharing MO₄ tetrahedra. The Bi₂Al₄O₉ and Bi₂Fe₄O₉ endmembers display single bands with maxima centred at 922 and 812 cm⁻¹, respectively. Intermediate Bi₂Al_4−x Fe _x O₉ compounds exhibit a distinct splitting into three relatively sharp bands, which is interpreted in terms of ordering effects within the tetrahedral pairs. Thereby the high-energy component band of the band triplet relates to Al–O–Al conjunctions and the low-energy component band to Fe–O–Fe conjunctions. The intermediate band is assigned to stretching vibrations of Al–O–Fe or Fe–O–Al configurations of the corner-sharing tetrahedral pairs. Bands in the 800–600 cm⁻¹ range are assigned to low-energy stretching vibrations of the MO₄ tetrahedra and to M–O–M bending vibrations of the tetrahedral pairs. Absorptions in the 600–400 cm⁻¹ range are essentially determined by M–O stretching modes of the M cations in octahedral coordination.  相似文献   

Hydroxyl in mantle olivine xenocrysts from the Udachnaya kimberlite pipe   总被引：6，自引：1，他引：5  

Monika Koch-Müller  Stanislav S. Matsyuk  Dieter Rhede  Richard Wirth  Natasha Khisina 《Physics and Chemistry of Minerals》2006,33(4):276-287

The incorporation of hydrogen in mantle olivine xenocrysts from the Udachnaya kimberlite pipe was investigated by Fourier-transform infrared spectroscopy and secondary ion mass spectrometry (SIMS). IR spectra were collected in the OH stretching region on oriented single crystals using a conventional IR source at ambient conditions and in situ at temperatures down to −180°C as well as with IR synchrotron radiation. The IR spectra of the samples are complex containing more than 20 strongly polarized OH bands in the range 3,730–3,330 cm⁻¹. Bands at high energies (3,730–3,670 cm⁻¹) were assigned to inclusions of serpentine, talc and the 10 Å phase. All other bands are believed to be intrinsic to olivine. The corresponding point defects are (a) associated with vacant Si sites (3,607 cm⁻¹ E || a, 3,597 E || a, 3,571 cm⁻¹ E || c, 3,567 E || c, and 3,556 E || b), and (b) with vacant M1 sites (most of the bands polarized parallel to a). From the pleochroic behavior and position of the OH bands associated with the vacant M1 sites, we propose two types of hydrogen—one bonded to O1 and another to O2, so that both OH vectors are strongly aligned parallel to a. The O2–H groups may be responsible for the OH bands at higher wavenumbers than those for the O1–H groups. The multiplicity of the corresponding OH bands in the spectra can be explained by different chemical environments and by slightly different distortions of the M1 sites in these high-pressure olivines. Four samples were investigated by SIMS. The calculated integral molar absorption coefficient using the IR and SIMS results of 37,500±5,000 L mol H₂O cm⁻² is within the uncertainties slightly higher than the value determined by Bell et al. (J Geophys Res 108(B2):2105–2113, 2003) (28,450±1,830 L mol H₂O cm⁻²). The reason for the difference is the different distributions of the absorption intensity of the spectra of both studies (mean wavenumber 3,548 vs. 3,570 cm⁻¹). Olivine samples with a mean wavenumber of about 3,548 cm⁻¹ should be quantified with the absorption coefficient as determined in this study; those containing more bands at higher wavenumber (mean wavenumber 3,570 cm⁻¹) should be quantified using the value determined by Bell et al. (J Geophys Res 108(B2):2105–2113, 2003).

Monika Koch-MüllerEmail: Phone: +49-331-2881492

  相似文献   

Dehydration process and structural development of cordierite ceramic precursors derived from FTIR spectroscopic investigations     

D. Voll  A. Beran 《Physics and Chemistry of Minerals》2002,29(8):545-551

 Cordierite precursors were prepared by a sol-gel process using tetraethoxysilane, aluminum sec.-butoxide, and Mg metal flakes as starting materials. The precursors were treated by 15-h heating steps in intervals of 100 °C from 200 to 900 °C; they show a continuous decrease in the analytical water content with increasing preheating temperatures. The presence of H₂O and (Si,Al)–OH combination modes in the FTIR powder spectra prove the presence of both H₂O molecules and OH groups as structural components, with invariable OH concentrations up to preheating temperatures of 500 °C. The deconvolution of the absorptions in the (H₂O,OH)-stretching vibrational region into four bands centred at 3584, 3415, 3216 and 3047 cm⁻¹ reveals non-bridging and bridging H₂O molecules and OH groups. The precursor powders remain X-ray amorphous up to preheating temperatures of 800 °C. Above this temperature the precursors crystallize to μ-cordierite; at 1000 °C the structure transforms to α-cordierite. Close similarities exist in the pattern of the 1400–400 cm⁻¹ lattice vibrational region for precursors preheated up to 600 °C. Striking differences are evident at preheating temperatures of 800 °C, where the spectrum of the precursor powder corresponds to that of conventional cordierite glass. Bands centred in the “as-prepared” precursor at 1137 and 1020 cm⁻¹ are assigned to Si–O-stretching vibrations. A weak absorption at 872 cm⁻¹ is assigned to stretching modes of AlO₄ tetrahedral units and the same assignment holds for a band at 783 cm⁻¹ which appears in precursors preheated at 600 °C. With increasing temperatures, these bands show a significant shift to higher wavenumbers and the Al–O stretching modes display a strong increase in their intensities. (Si,Al)–O–(Si,Al)-bending modes occur at 710 cm⁻¹ and the band at 572 cm⁻¹ is assigned to stretching vibrations of AlO₆ octahedral units. A strong band around 440 cm⁻¹ is essentially attributed to Mg–O-stretching vibrations. The strongly increasing intensity of the 872 and 783 cm⁻¹ bands demonstrates a clear preference of Al for a fourfold-coordinated structural position in the precursors preheated at high temperatures. The observed band shift is a strong indication for increasing tetrahedral network condensation along with changes in the Si–O and Al–O distances to tetrahedra dimensions similar to those occurring in crystalline cordierite. These structural changes are correlated to the dehydration process starting essentially above 500 °C, clearly demonstrating the inhibiting role of H₂O molecules and especially of OH groups. Received: 1 March 2002 / Accepted: 26 June 2002  相似文献   

High-temperature X-ray diffraction and Raman spectroscopy of diopside and pseudowollastonite     

Pascal Richet  Bjorn O. Mysen  Jannick Ingrin 《Physics and Chemistry of Minerals》1998,25(6):401-414

Diopside (CaMgSi₂O₆) and pseudowollastonite (CaSiO₃) have been studied by X-ray powder diffraction and Raman spectroscopy up to their respective melting points. In agreement with previous unit-cell parameters determinations below 1100 K, thermal expansion of diopside along the a and c axis is much smaller than along the b axis. For pseudowollastonite, the axis expansivity increases slightly in the order b>a>c. For both minerals, the change in unit-cell angles is very small and there are no anomalous variations of the other unit-cell parameters near the melting point. With increasing temperatures, the main changes observed in the Raman spectra are strong increases of the linewidths for those bands which mainly represent Si−O−Si bending (near 600 cm⁻¹) or involve Ca−O or Mg−O stretching, in the range 270–500 cm⁻¹ for diopside, and 240–450 cm⁻¹ for pseudowollastonite. At temperatures near the onset of calorimetric premelting effects, this extensive band widening results in a broad Raman feature that can no longer be deconvoluted into its individual components. No significant changes affect the Si−O streching modes. For both diopside and pseudowollastonite, premelting appears to be associated with enhanced dynamics of the alkaline-earth elements. This conclusion contrasts markedly with that drawn for sodium metasilicate in which weaker bonding of sodium allows the silicate framework to distort and deform in such a way as to prefigure the silicate entities present in the melt. Received 16 July 1997 / Revised, accepted: 6 March 1998  相似文献   

High-pressure Raman spectroscopic study of Fo90 hydrous wadsleyite     

Annette K. Kleppe  Andrew P. Jephcoat  Joseph R. Smyth 《Physics and Chemistry of Minerals》2006,32(10):700-709

Raman spectra of monoclinic Fo₉₀ hydrous wadsleyite with 2.4 wt% H₂O have been measured in a diamond-anvil cell with helium as a pressure-transmitting medium to 58.4 GPa at room temperature. The most intense, characteristic wadsleyite modes, the Si–O–Si symmetric stretch at 721 cm⁻¹ and the symmetric stretch of the SiO₃ unit at 918 cm⁻¹, shift continuously to 58.4 GPa showing no evidence of a first order change in the crystal structure despite compression well beyond the stability field of wadsleyite in terms of pressure. The pressure dependence of these two modes is nearly identical for Fo₉₀ hydrous and Fo₁₀₀ anhydrous wadsleyite. A striking feature in the high-pressure Raman spectra of Fo₉₀ hydrous wadsleyite is the appearance of new Raman modes above 9 GPa in the mid-frequency range (300–650 cm⁻¹ at 1-bar and shifted to 500–850 cm⁻¹ at 58.4 GPa) accompanied by a significant growth in their intensities under further compression. In the OH stretching frequency range Fo₉₀ hydrous wadsleyite exhibits a larger number of modes than the Mg end-member phase. The higher number of modes may be due to either additional protonation sites or simply that we observe a different subset of all possible OH modes for each sample. The high-pressure behaviour of the OH stretching modes of Fo₉₀ and Fo₁₀₀ hydrous wadsleyite is consistent: OH stretching modes with frequencies <3,530 cm⁻¹ decrease with increasing pressure whereas the higher-frequency OH modes show a close to constant pressure dependence to at least 13.2 GPa. The approximately constant pressure dependence of the OH modes above 3,530 cm⁻¹ is consistent with protons being located at the O1···O edges around M3.  相似文献   

A hitherto unrecognised band in the Raman spectra of silica rocks: influence of hydroxylated Si–O bonds (silanole) on the Raman moganite band in chalcedony and flint (SiO<Subscript>2</Subscript>)     

Patrick?SchmidtEmail author  Ludovic?Bellot-Gurlet  Aneta?Slodczyk  Fran?ois?Fr?hlich 《Physics and Chemistry of Minerals》2012,39(6):455-464

Chalcedony is a spatial arrangement of hydroxylated nanometre-sized α-quartz (SiO₂) crystallites that are often found in association with the silica mineral moganite (SiO₂). A supplementary Raman band at 501 cm⁻¹ in the chalcedony spectrum, attributed to moganite, has been used for the evaluation of the quartz/moganite ratio in silica rocks. Its frequency lies at 503 cm⁻¹ in sedimentary chalcedony, representing a 2 cm⁻¹ difference with its position in pure moganite. We present a study of the 503 cm⁻¹ band’s behaviour upon heat treatment, showing its gradual disappearance upon heating to temperatures above 300 °C. Infrared spectroscopic measurements of the silanole (SiOH) content in the samples as a function of annealing temperature show a good correlation between the disappearance of the 503 cm⁻¹ Raman band and the decrease of structural hydroxyl. Thermogravimetric analyses reveal a significant weight loss that can be correlated with the decreasing of this Raman band. X-ray powder diffraction data suggest the moganite content in the samples to remain stable. We propose therefore the existence of a hitherto unknown Raman band at 503 cm⁻¹ in chalcedony, assigned to ‘free’ Si–O vibrations of non-bridging Si–OH that oscillate with a higher natural frequency than bridging Si–O–Si (at 464 cm⁻¹). A similar phenomenon was recently observed in the infrared spectra of chalcedony. The position of this Si–OH-related band is nearly the same as the Raman moganite band and the two bands may interfere. The actually observed Raman band in silica rocks might therefore be a convolution of a silanole and a moganite vibration. These findings have broad implications for future Raman spectroscopic studies of moganite, for the assessment of the quartz/moganite ratio, using this band, must take into account the contribution from silanole that are present in chalcedony and moganite.  相似文献   

Thermal behaviour and kinetics of dehydration of gypsum in air from in situ real-time laboratory parallel-beam X-ray powder diffraction     

Paolo Ballirano  Elisa Melis 《Physics and Chemistry of Minerals》2009,36(7):391-402

Thermal behaviour and kinetics of dehydration of gypsum in air have been investigated using in situ real-time laboratory parallel-beam X-ray powder diffraction data evaluated by the Rietveld method. Thermal expansion has been analysed from 298 to 373 K. The high-temperature limits for the cell edges and for the cell volume, calculated using the Einstein equation, are 4.29 × 10⁻⁶, 4.94 × 10⁻⁵, 2.97 × 10⁻⁵, and 8.21 × 10⁻⁵. Thermal expansion of gypsum is strongly anisotropic being larger along the b axis mainly due to the weakening of hydrogen bond. Dehydration of gypsum has been investigated in isothermal conditions within the 348–403 K range with a temperature increase of 5 K. Dehydration proceeds through the CaSO₄·2H₂O → CaSO₄·0.5H₂O → γ-CaSO₄ steps. Experimental data have been fitted with the Avrami equation to calculate the empirical activation energy of the process. No change in transformation mechanism has been observed within the analysed temperature range and the corresponding E _a is 109(12) kJ/mol.  相似文献   

Mechanisms of OH defect incorporation in naturally occurring,hydrothermally formed diopside and jadeite     

M. Andrut  M. Wildner  J. Ingrin  A. Beran 《Physics and Chemistry of Minerals》2007,34(8):543-549

The IR spectrum of an alpine, hydrothermally formed diopside containing 17 wt ppm H₂O consists of three main OH absorption bands centred at 3647, 3464 and 3359 cm⁻¹. Jadeite from a Californian vein occurrence is characterised by bands at 3616 and 3557 cm⁻¹ and contains about 197 wt ppm H₂O. Based on the pleochroic scheme of the OH absorption bands in diopside, OH defect incorporation models are derived on the basis of fully occupied cation sites and under the assumption of M1 and M2 site vacancies; OH defects replacing O2 oxygen atoms are most common. The less pronounced OH pleochroism and the broad band absorption pattern of jadeite indicate a high degree of OH defect disordering. The pleochroic scheme of the main absorption bands at 3616 and 3557 cm⁻¹ implies partial replacement of O2 oxygen atoms by OH dipoles pointing to vacant Si sites. Under the assumption of M1 and M2 site vacancies, O1–H and O2–H defects are also derivable. OH incorporation modes assuming Si-vacancies should be considered for jadeite-rich clinopyroxenes formed in deep crust and upper mantle regions.  相似文献   

Synchrotron IR study of hydrous ringwoodite (γ-Mg2SiO4) up to 30 GPa     

E. M. Chamorro Pérez  I. Daniel  J.-C. Chervin  P. Dumas  J. D. Bass  T. Inoue 《Physics and Chemistry of Minerals》2006,33(7):502-510

High-pressure synchrotron infrared (IR) absorption spectra were collected between 650 and 4,000 cm⁻¹ at ambient temperature for hydrous Mg-ringwoodite (γ-Mg₂SiO₄) up to 30 GPa. The main feature in the OH⁻ stretching region is an extremely broad band centred at 3,150 cm⁻¹. The hydrogen bond is strong for most protons and the most probable site for protonation is the tetrahedral edge. With increasing pressure, this band shifts downward while decreasing its integrated intensity until disappearance at a pressure of 25 GPa. Only one band at 2,450 cm⁻¹ and an absorption plateau persist with a maximum wavenumber of 3,800 cm⁻¹. This behaviour is reversible upon pressure release. We interpret this as a second-order phase transition occurring in hydrated Mg-ringwoodite at high pressure (beyond ∼ 25 GPa). This result is compatible with the observation by Kleppe et al. (Phys Chem Miner 29:473–476, 2002a) who suggested the presence of Si–O–Si linkages and/or partial increase in the coordination of Si. Beyond the phase transition, the protons are delocalized and their environment on the ringwoodite structure is probably quite different from that at low pressure. Data obtained in situ at high pressures and temperatures are needed to better understand the effect of protonation on the structure and to better constrain this phase transition.  相似文献   

Thermal expansion and decomposition of jarosite: a high-temperature neutron diffraction study     

Hongwu Xu  Yusheng Zhao  Sven C. Vogel  Donald D. Hickmott  Luke L. Daemen  Monika A. Hartl 《Physics and Chemistry of Minerals》2010,37(2):73-82

The structure of deuterated jarosite, KFe₃(SO₄)₂(OD)₆, was investigated using time-of-flight neutron diffraction up to its dehydroxylation temperature. Rietveld analysis reveals that with increasing temperature, its c dimension expands at a rate ~10 times greater than that for a. This anisotropy of thermal expansion is due to rapid increase in the thickness of the (001) sheet of [Fe(O,OH)₆] octahedra and [SO₄] tetrahedra with increasing temperature. Fitting of the measured cell volumes yields a coefficient of thermal expansion, α = α₀ + α₁ T, where α₀ = 1.01 × 10⁻⁴ K⁻¹ and α₁ = −1.15 × 10⁻⁷ K⁻². On heating, the hydrogen bonds, O1···D–O3, through which the (001) octahedral–tetrahedral sheets are held together, become weakened, as reflected by an increase in the D···O1 distance and a concomitant decrease in the O3–D distance with increasing temperature. On further heating to 575 K, jarosite starts to decompose into nanocrystalline yavapaiite and hematite (as well as water vapor), a direct result of the breaking of the hydrogen bonds that hold the jarosite structure together.  相似文献   

The single-crystal,polarized-light,FTIR spectrum of stoppaniite,the Fe analogue of beryl     

Giancarlo Della Ventura  Fabio Bellatreccia  Paolo Rossi 《Physics and Chemistry of Minerals》2007,34(10):727-731

We report here a single-crystal polarized-light study of stoppaniite, ideally (Fe,Al,Mg)₄(Be₆Si₁₂O₃₆)(H₂O)₂(Na,□), from Capranica (Viterbo). Polarized-light FTIR spectra were collected on an oriented (hk0) section, doubly polished to 15 μm. The spectrum shows two main bands at 3,660 and 3,595 cm⁻¹; the former is strongly polarized for E ⊥c, while the latter is polarized for E //c. A sharp and very intense band at 1,620 cm⁻¹, plus minor features at 4,000 and 3,228 cm⁻¹ are also polarized for E //c. On the basis of literature data and considering the pleochroic behavior of the absorptions, the 3,660 cm⁻¹ band is assigned to the ν₃ stretching mode and the 1,620 cm⁻¹ (associated with an overtone 2*ν₂ at 3,230 cm⁻¹) band to the ν₂ bending mode of “type II” water molecules within the structural channels of the studied beryl. The sharp band at 3,595 cm⁻¹ is not associated with a corresponding ν₂ bending mode; thus it is assigned to the stretching vibration of O–H groups in the sample. The minor 4,000 cm⁻¹ feature can be assigned to the combination of the O–H bond parallel to c with a low-frequency metal-oxygen mode such as the Na–O stretching mode. The present results suggest that the interpretation of the FTIR spectrum of Na-rich beryl needs to be carefully reconsidered.  相似文献   

Intercalation of kaolinite with acetamide     

R. L. Frost  J. Kristof  G. N. Paroz  J. T. Kloprogge 《Physics and Chemistry of Minerals》1999,26(3):257-263

Upon intercalation of both ordered (low defect) and disordered (high defect) kaolinites with acetamide, two types of interaction are observed. Firstly, hydrogen bonding between the NH₂ groups of the acetamide with the siloxane oxygens is formed, as evidenced by the formation of two new bands at 3400 and 3509 cm^–1. Secondly, the appearance of additional bands at ∼3600 cm^–1 in both the infrared and Raman spectra of the acetamide intercalates is attributed to a second type of hydrogen bonding by the interaction of the C=O group and the inner surface hydroxyls. Changes in the intensity of the hydroxyl deformation modes in the 895 to 940 cm^–1 region are attributed to the changes in the hydrogen bonding of the kaolinite surfaces. It is proposed that the hydrogen bonding between the adjacent kaolinite layers is replaced with hydrogen bonding between both kaolinite surfaces and the acetamide molecule. Changes in the molecular structure of acetamide are observed upon intercalation. The amide 1 band is lost and replaced with a well-defined NH₂ deformation vibration. The loss of the amide 1 band is attributed the hydrogen bond formation between the amide hydrogens and the siloxane surface. The bands of the C=O group at 1680 and 1740 cm^–1 become a single band at 1680 cm^–1. The amide 2 band remains unchanged. The lack of intensity of the 1740 cm^–1 band is attributed to the formation of hydrogen bonding between the inner surface hydroxyl groups and the carbonyl group. Received: 4 February 1998/ Revised, accepted: 30 June 1998  相似文献   

A Raman spectroscopic investigation of Fe-rich sphalerite: effect of fe-substitution     

Sherif Kharbish 《Physics and Chemistry of Minerals》2007,34(8):551-558

A Raman spectroscopic study of Fe-rich sphalerite (Zn_{1 − x} Fe _x S) has been carried out for six samples with 0.10 ≤ x ≤ 0.24. Both the intensities and frequencies of the TO and LO modes of sphalerite are approximately independent of Fe concentration. However, the substitution of Zn by Fe results in five additional bands with frequencies between the TO (271 cm⁻¹) and LO (350 cm⁻¹) modes. Three of these bands are attributed to resonance modes (i.e. Y ₁, Y ₂ and Y ₃ modes). The fourth band (B mode) is assigned to a breathing mode of the nearest-neighbor sulfur atoms around the Fe atoms. The band at 337 cm⁻¹ is attributed to the presence of Fe³⁺. The excellent correlations between the normalized intensities of these five different modes and x _Fe show that these modes depend on Fe-content. Another extra mode at 287 cm⁻¹ is assigned to the presence of Cd in sphalerite.  相似文献   

The Kinetics of the Interaction Between Iron(III)-Ethylenediaminetetraacetate and Peroxynitrite     

Virender K. Sharma  Ria A. Yngard  Zoltan Homonnay  Abhishek Dey  Chun He 《Aquatic Geochemistry》2010,16(3):483-490

The kinetics of the formation of the purple-colored species between Fe^III-EDTA and peroxynitrite were studied as a function of pH (10.4–12.3) at 22°C in aqueous solutions using a stopped-flow technique. A purple-colored species was immediately formed upon mixing, which had an absorbance maximum at 520 nm. The increase in absorbance with time could be fit empirically by a power function with two parameters a and b. The power equation determined was absorbance = a*t ^b , where a increased linearly with pH and the concentration of peroxynitrite, while b almost remained constant with a value of ~0.25. The molar extinction coefficient ε_520 nm for the colored species was determined as 13 M⁻¹cm⁻¹, which is much lower than ε_520 nm = 520 M⁻¹ cm⁻¹ for the [Fe^III(EDTA)O₂]³⁻, a purple species observed in the Fe^III–EDTA–H₂O₂ system. The results of kinetics and spectral measurements of the present study are briefly discussed and compared with those of the reaction between Fe(III)-EDTA and hydrogen peroxide.  相似文献   

Infrared spectroscopic characterization of dehydration and accompanying phase transition behaviors in NAT-topology zeolites     

Hsiu-Wen?WangEmail author  David?L.?Bish 《Physics and Chemistry of Minerals》2012,39(4):277-293

Relative humidity ( P_{\textH 2 \textO} P_{{{\text{H}}_{ 2} {\text{O}}}} , partial pressure of water)-dependent dehydration and accompanying phase transitions in NAT-topology zeolites (natrolite, scolecite, and mesolite) were studied under controlled temperature and known P_{\textH 2 \textO} P_{{{\text{H}}_{ 2} {\text{O}}}} conditions by in situ diffuse-reflectance infrared Fourier transform spectroscopy and parallel X-ray powder diffraction. Dehydration was characterized by the disappearance of internal H₂O vibrational modes. The loss of H₂O molecules caused a sequence of structural transitions in which the host framework transformation path was coupled primarily via the thermal motion of guest Na⁺/Ca²⁺ cations and H₂O molecules. The observation of different interactions of H₂O molecules and Na⁺/Ca²⁺ cations with host aluminosilicate frameworks under high- and low- P_{\textH 2 \textO} P_{{{\text{H}}_{ 2} {\text{O}}}} conditions indicated the development of different local strain fields, arising from cation–H₂O interactions in NAT-type channels. These strain fields influence the Si–O/Al–O bond strength and tilting angles within and between tetrahedra as the dehydration temperature is approached. The newly observed infrared bands (at 2,139 cm⁻¹ in natrolite, 2,276 cm⁻¹ in scolecite, and 2,176 and 2,259 cm⁻¹ in mesolite) result from strong cation–H₂O–Al–Si framework interactions in NAT-type channels, and these bands can be used to evaluate the energetic evolution of Na⁺/Ca²⁺ cations before and after phase transitions, especially for scolecite and mesolite. The 2,176 and 2,259 cm⁻¹ absorption bands in mesolite also appear to be related to Na⁺/Ca²⁺ order–disorder that occur when mesolite loses its Ow4 H₂O molecules.  相似文献   

Visualization-based analysis of structural and dynamical properties of simulated hydrous silicate melt     

Bijaya B. Karki  Dipesh Bhattarai  Mainak Mookherjee  Lars Stixrude 《Physics and Chemistry of Minerals》2010,37(2):103-117

We have explored first-principles molecular dynamics simulation data for hydrous MgSiO₃ liquid (with 10 wt% water) to gain insight into its structural and dynamical behavior as a function of pressure (0–150 GPa) and temperature (2,000–6,000 K). By visualizing/analyzing a number of parameters associated with short- and mid-range orders, we have shown that the melt structure changes substantially on compression. The speciation of the water component at low pressures is dominated by the isolated structures (with over 90% hydrogen participated) consisting of hydroxyls, water molecules, O–H–O bridging and four-atom (O–H–O–H and H–O–H–O) groups, where every oxygen atom may be a part of polyhedron or free (i.e., bound to only magnesium atom). Hydroxyls favor polyhedral sites over magnesium sites whereas molecular water is almost entirely bound to magnesium sites, and also interpolyhedral bridging (Si–O–H–O–Si) dominates other types of bridging. Water content is shown to enhance and suppress, respectively, the proportions of hydroxyls and molecular water. As compression increases, these isolated structures increasingly combine with each other to form extended structures involving a total of five or more O and H atoms and also containing threefold coordination species, which together consume over 80% hydrogen at the highest compression studied. Our results show that water lowers the mean coordination numbers of different types including all cation–anion environments. The hydrous melt tends to be more tetrahedrally coordinated but with the Si–Si network being more disrupted compared to the anhydrous melt. Protons increase the content of non-bridging oxygen and decrease the contents of bridging oxygen as well as oxygen triclusters (present at pressures above 10 GPa). The calculated self-diffusion coefficients of all atomic species are enhanced in the presence of water compared to those of the anhydrous melt. This is consistent with the prediction that water depolymerizes the melt structure at all pressures. Our analysis also suggests that proton diffusion involves two processes—the transfer of H atoms (requiring the rupture and formation of O–H bonds) and the motion of hydroxyls as hydrogen carriers (requiring the rupture and formation of Si–O and/or Mg–O bonds). Both the processes are operative at low compression whereas only the first process is operative at high compression.  相似文献   

Comparison of Measured and PTF Predictions of SWCCs for Loess Soils in China   总被引：1，自引：0，他引：1  

Mingbin Huang  D. G. Fredlund  M. D. Fredlund 《Geotechnical and Geological Engineering》2010,28(2):105-117

There are significant advantages in using indirect pedo-transfer functions, (PTFs) for the estimation of unsaturated soil properties. The pedo-transfer functions can be used for the estimation of the soil–water characteristic curve (SWCC) which in turn is used for the estimation of other unsaturated soil properties. The accuracy of the indirect pedo-transfer function method for the estimation of the SWCC depends on the PTF and the equation used to best-fit the particle-size distribution (PSD) data. The objectives of this study are to: (1) evaluate the performance of the Fredlund et al. (Can Geotech J 37:817–827, 2000) equation for best-fitting the particle-size distribution, (PSD) data, and, (2) compare the predictions made by two of the commonly used PTFs; namely, Arya and Paris (Soil Sci Soc Am J 45:1023–1030, 1981) and Fredlund et al. (Can Geotech J 39:1103–1117, 2002), for estimating the SWCC from the PSD. The authors used 258 measured PSDs and SWCC datasets from the Loess Plateau, China, for this study. The dataset consisted of 187 silt–loam soils, 41 loam soils, 11 silt–clay–loam soils, 10 sand–loam soils, 6 silt–clay soils, and 3 loam–sand soils. The SWCC and PSD datasets were measured using a Pressure Plate apparatus and the pipette method, respectively. The comparison between the estimated and measured particle-size distribution curves showed that the Fredlund et al. (Can Geotech J 37:817–827, 2000) equation closely prepresented the PSD for all soils in the Loess Plateau, with a lower root mean square error (RMSE) of 0.869%. The comparison between the estimated and measured water contents at the same suction showed that the Fredlund et al. (Can Geotech J 39:1103–1117, 2002) PTF performed somewhat better than the Arya and Paris (Soil Sci Soc Am J 45:1023–1030, 1981) function. The Fredlund et al. method had RMSE value of 0.039 cm³ cm⁻³ as opposed to 0.046 cm³ cm⁻³ for the Arya and Paris (Soil Sci Soc Am J 45:1023–1030, 1981) method. The Fredlund et al. (Can Geotech J 39:1103–1117, 2002) PTF produced the closest predictions for sand–loam, loam–sand, and loam soils, with a lower RMSE for gravimetric water content ranging from 0.006 to 0.036 cm³ cm⁻³. There were consistent over-estimations observed for silt–loam, silt–clay–loam, and slit–clay soils with RMSE values for gravimetric water content ranging from 0.037 to 0.043 cm³ cm⁻³. The measured and estimated air-entry values were closest when using the Fredlund et al. (Can Geotech J 39:1103–1117, 2002) PTF. The measured and estimated maximum slopes on the SWCC were closest when using the Arya and Paris (Soil Sci Soc Am J 45:1023–1030, 1981) PTF.  相似文献