Raman spectroscopy of natural cordierite at high water pressure up to 5 GPa

The high‐pressure behaviour of cordierite, a widespread ring aluminosilicate with channels incorporating fluid compounds (H₂O, CO₂), is characterized by the absence of phase transitions up to 2.5 GPa. However, the distortion of the ring tetrahedra observed previously at 2.3 GPa is supposed to introduce a phase transition at higher pressure, which has not been checked so far. This work presents a high‐pressure Raman spectroscopic study of natural cordierite compressed in water medium up to 4.7 GPa in a diamond anvil cell. At P > 4 GPa, a disordering of both the framework and intrachannel H₂O subsystem is apparent from significant broadening of Raman peaks and the evolution of short‐range order parameters. This is followed by abrupt shifts of the framework and O–H stretching modes at about 4.5 GPa, indicating a first‐order phase transition. Its reversibility is seen from the recovery of the initial spectrum at P < 3 GPa. The shift amplitudes of different framework modes indicate the predominance of distortion over contraction of the framework polyhedra upon this transition. The disordering of the H₂O subsystem in the high‐pressure phase is likely a consequence of distortion of the channel‐forming framework elements, which is supposed to be a driving force of this transition. Copyright © 2011 John Wiley & Sons, Ltd.     

Formation of the high pressure graphite and BC8 phases in a cold compression experiment by Raman scattering

We use Raman scattering to study phase transition in the graphitic g‐BC₈ phase and graphite at high pressure up to 84 GPa. The E_2g Raman active mode of graphite (G peak) can be detected up to 84 GPa. We demonstrate that there is (1) a phase transition in g‐BC₈ and in graphite at 35 GPa and (2) that above 35 GPa, the g‐BC₈ and graphite transform under high pressure to possibly fully sp³‐bonded, disordered hp‐BC₈, and hp‐C phases. Below the phase transition, a polynomial fit to the G peak position versus pressure data yielded a quadratic relation; above the phase transition, it demonstrates linear behavior. The phase transition at high pressure in BC₈ system and graphite is reversible. Quenched hp‐BC₈ and hp‐C phases have the Raman spectrum typical to that of the graphitic phases. Copyright © 2013 John Wiley & Sons, Ltd.     

Raman spectroscopy of melamine at high pressures up to 60 GPa

In this work, the Raman scattering of melamine was studied under high pressure up to 60 GPa. The behavior of the most intensive peaks of the Raman spectrum of melamine, 677 cm^?1 and 985 cm^?1 modes, and their line widths do not show any phase transition or indication of formation of sp ³ bonds. Comparing the behavior of the line width of the Raman peaks of graphite under pressure and that of melamine leads us to conclude that the s-triasine (C–N) ring is more rigid than the C–C graphite ring. High pressure results with melamine suggest that the direct phase transition g-C₃N₄ to dense C₃N₄ phase should occur above 60 GPa.     

A high pressure Raman study of TeO2 to 30 GPa and pressure-induced phase changes

The effect of pressure on the Raman modes in TeO₂ (paratellurite) has been investigated to 30GPa, using the diamond cell and argon as pressure medium. The pressure dependence of the Raman modes indicates four pressure-induced phase transitions near 1 GPa, 4.5 GPa, 11 GPa and 22 GPa. Of these the first is the well studied second-order transition fromD ₄ ⁴ symmetry toD ₂ ⁴ symmetry, driven by a soft acoustic shear mode instability. The remarkable similarity in the Raman spectra of phases I to IV suggest that only subtle changes in the structure are involved in these phase transitions. The totally different Raman spectral features of phase V indicate major structural changes at the 22GPa transition. It is suggested that this high pressure-phase is similar to PbCl₂-type, from high pressure crystal chemical considerations. The need for a high pressure X-ray diffraction study on TeO₂ is emphasized, to unravel the structure of the various high pressure phases in the system.     

Hydrogen‐bonding interactions in fully deuterated α‐glycine at high pressures

Recent spectroscopic investigations of various amino acids report intriguing high‐pressure and low‐temperature behavior of NH₃⁺ groups and their influence on various hydrogen bonds in the system. In particular, the variation of the intensity of NH₃⁺ torsional mode at different temperatures and pressures has received much attention. We report here the first in situ Raman investigations of fully deuterated α‐glycine up to ∼20 GPa. The discontinuous changes in COO⁻ and ND₃⁺ modes across ∼3 GPa indicate subtle structural rearrangements in fully deuterated α‐glycine. The decrease in the intensity of ND₃⁺ torsional mode is found to be similar to that of undeuterated α‐glycine. The pressure‐induced stiffening of N D and CD₂ stretching modes are discussed in the context of changes in the hydrogen‐bonding interactions. Copyright © 2011 John Wiley & Sons, Ltd.     

Raman study of datolite CaBSiO4(OH) at simultaneously high pressure and high temperature

Using an in situ method of Raman spectroscopy and resistance‐heated diamond anvil cell, the system datolite CaBSiO₄(OH) – water has been investigated at simultaneously high pressure and temperature (up to Р ~5 GPa and Т ~250 °С). Two polymorphic transitions have been observed: (1) pressure‐induced phase transition or the feature in pressure dependence of Raman band wavenumbers at P = 2 GPа and constant T = 22 °С and (2) heating‐induced phase transition at T ~90 °С and P ~5 GPа. The number of Raman bands is retained at the first transition but changed at the second transition. The first transition is mainly distinguished by the changes in the slopes of pressure dependence of Raman peaks at 2 GPa. The second transition is characterized by several strong changes: the wavenumber jumps of major bands, the merging of strong doublets at 378 and 391 cm⁻¹ (values for ambient conditions), the splitting of the intermediate‐intensity band at 292 cm⁻¹, and the transformation of some low‐wavenumber bands at 160–190 cm⁻¹. No spectral and visual signs of overhydration and amorphization have been observed. No noticeable dissolution of datolite in the water medium occurred at 5 GPa and 250 °С after 3 h, which corresponds to typical conditions of the ‘cold’ zones of slab subduction. Copyright © 2014 John Wiley & Sons, Ltd.     

In situ Raman and photoluminescence study on pressure‐induced phase transition in C60 nanotubes

Single crystalline C₆₀ nanotubes having face‐centered‐cubic structure with diameters in the nanometer range were synthesized by a solution method. In situ Raman and photoluminescence spectroscopy under high pressure were employed to study the structural stabilities and transitions of the pristine C₆₀ nanotubes. A phase transition, probably because of the orientational ordering of C₆₀ molecules, from face‐centered‐cubic structure to simple cubic structure occurred at the pressure between 1.46 and 2.26 GPa. At above 20.41 GPa, the Raman spectrum became very diffuse and lost its fine structure in all wavenumber regions, and only two broad and asymmetry peaks initially centered at 1469 and 1570 cm^–1 were observed, indicating an occurrence of amorphization. This amorphous phase remained to be reversible until 31.1 GPa, and it became irreversible to the ambient pressure after the pressure cycle of 34.3 GPa was applied. Copyright © 2012 John Wiley & Sons, Ltd.     

Raman study of thaumasite Ca3Si(OH)6(SO4)(CO3)⋅12H2O at high pressure

Thaumasite, Ca₃Si(OH)₆(SO₄)(CO₃)⋅12H₂O, is an extraordinary mineral that possibly plays a special role in the carbonate–sulfate–silicate balance of the Earth's crust. Thaumasite, an undesirable component in concrete, remains a material poorly studied at high pressures in various media except for He medium (M. Ardit et al., Mineral. Mag., 2014). In the present Raman study, thaumasite samples were compressed in alcohol–water and KBr media at high pressures up to ~7 GPa: several phase transformations were identified. In samples compressed in alcohol–water, the wavenumbers of intense Raman bands of S O and С О symmetric stretching vibrations at 991 and 1074 cm⁻¹ proved to exhibit similar dependences on pressure: during a first transition I → II at 4.4 GPa, the wavenumbers of both bands exhibited a downward jump; at a second transition II → III, which occurred at 4.9 GPa, each band split in a doublet; and then, at a third transition III → IV, which was observed at 5.4 GPa, each doublet band transformed in a singlet. In KBr medium, these and other Raman bands of thaumasite showed similar (to those in thaumasite at compression in alcohol–water) dependences on pressure, revealing several phase transitions with slightly shifted transition points, the first transition I → II, however, being not distinguished. Taking into account the similar behaviors in both media, the transitions are assumed to be polymorphic: no noticeable overhydration in thaumasite compressed in water–alcohol occurred. In phase IV, gradual widening and weakening of each band were observed; those changes can be attributed to amorphization of the material. Considerable hysteresis was observed at thaumasite decompression. Copyright © 2016 John Wiley & Sons, Ltd.     

Pressure‐induced anomalous phase transformation in nano‐crystalline dysprosium sesquioxide

The phase transformation in nano‐crystalline dysprosium sesquioxide (Dy₂O₃) under high pressures is investigated using in situ Raman spectroscopy. The material at ambient was found to be cubic in structure using X‐ray diffraction (XRD) and Raman spectroscopy, while atomic force microscope (AFM) showed the nano‐crystalline nature of the material which was further confirmed using XRD. Under ambient conditions the Raman spectrum showed a predominant cubic phase peak at 374 cm⁻¹, identified as F_g mode. With increase in the applied pressure this band steadily shifts to higher wavenumbers. However, around a pressure of about 14.6 GPa, another broad band is seen to be developing around 530 cm⁻¹ which splits into two distinct peaks as the pressure is further increased. In addition, the cubic phase peak also starts losing intensity significantly, and above a pressure of 17.81 GPa this peak almost completely disappears and is replaced by two strong peaks at about 517 and 553 cm⁻¹. These peaks have been identified as occurring due to the development of hexagonal phase at the expense of cubic phase. Further increase in pressure up to about 25.5 GPa does not lead to any new peaks apart from slight shifting of the hexagonal phase peaks to higher wavenumbers. With release of the applied pressure, these peaks shift to lower wavenumbers and lose their doublet nature. However, the starting cubic phase is not recovered at total release but rather ends up in monoclinic structure. The factors contributing to this anomalous phase evolution would be discussed in detail. Copyright © 2010 John Wiley & Sons, Ltd.     

Infrared study of hydrogen up to 310 GPa at room temperature

We observed a strong difference of the pressure dependence of the infrared (IR) active molecular vibron of hydrogen in phase IV in the 200–310 GPa pressure range in comparison with the Raman vibrons. While the Raman vibron strongly splits (～250 cm^?1) at the transition from phases III to IV at 220 GPa, the IR vibron nearly does not change. This small spitting of IR vibron is not described by the graphene-like structure proposed for phase IV. The combined pressure dependence of Raman and IR vibrons provides a sensitive test for further theoretical models of phase IV.     

Photo-and pressure-induced transformations in the linear orthorhombic polymer of C<Subscript>60</Subscript>

Stability of the linear orthorhombic polymer of C₆₀ under pressure and laser irradiation is studied by Raman scattering and X-ray diffraction measurements. The Raman spectrum at ambient pressure remains unchanged, in the time scale of the experiment, up to an intensity of 3200 W/cm² of the 514.5 nm line of an Ar⁺ laser, but irreversible changes are observed at higher intensities. The Raman spectra recorded at increased pressure show similar irreversible changes even at the laser intensity as low as 470 W/cm². The X-ray diffraction and Raman measurements of the pressure-treated samples, performed after pressure release, show that the nonirradiated material does not exhibit any changes in the crystal structure and phonon spectra. This behavior indicates a pressure-enhanced photo-induced transformation to a new polymeric phase characterized by a Raman spectrum that differs from those of the other known polymeric phases of C₆₀. The Raman spectra of the phototransformed linear orthorhombic polymer of C₆₀ were measured at a pressure of up to 29 GPa. The pressure dependence of the Raman mode frequencies show singularities near 4 GPa and 15 GPa, respectively, related to a reversible phase transition and an irreversible transformation to a metastable disordered phase. The diffuse Raman spectrum of the disordered phase does not exhibit substantial changes with an increase in pressure up to 29 GPa. The high-pressure phase transforms to a mixture of pristine and dimerized C₆₀, after pressure release and exposure to ambient conditions for 30 h. The text was submitted by the authors in English.     

Elastic properties study of single crystal NH3 up to 26 GPa

Single crystal Brillouin and Raman scattering measurements on NH₃ in a diamond anvil cell have been performed under pressures up to 26 GPa at room temperature. The pressure dependencies of acoustic velocity, adiabatic elastic constants, and bulk moduli of ammonia from liquid to solid III and solid IV phase have been determined. All the nine elastic constants in orthorhombic structure phase IV were presented for the first time, each elastic constant grows monotonously with pressure and a crossover of the off‐diagonal moduli C₁₂ and C₁₃ was observed at around 12 GPa because of their different pressure derivative values. We also performed ab initio simulations to calculate the bulk elastic moduli for orthorhombic ammonia, the calculated bulk moduli agree well with experimental results. In Raman spectra the very weak bending modes ν₂ and ν₄ for orthorhombic ammonia are both observed at room temperature, a transition point near 12 GPa is also found from the pressure evolution of the Raman bands. Copyright © 2011 John Wiley & Sons, Ltd.     

High‐pressure Raman spectra of deuterated L‐alanine crystal

Raman spectra of deuterated L ‐alanine have been obtained at high‐pressure conditions. A phase transition at ∼1.5 GPa associated with the splitting of some internal modes and increase of the wavenumber of the external modes was observed. Similarly to the hydrogenated L ‐alanine crystal, this first transition was related to a symmetry change. Moreover, further modifications of the Raman spectra were observed at 4.4 GPa, which may be associated to conformational changes of the molecule. To give further support to such a hypothesis, neutron powder diffraction measurements were performed. Information about the cell parameter at atmospheric pressure gave valuable information about the N D distances, shedding light on the behavior of the torsional vibration of ND₃⁺. Copyright © 2009 John Wiley & Sons, Ltd.     

High pressure Raman spectra of L‐methionine crystal

Raman spectra of an L ‐methionine (C₅H₁₁NO₂S) crystal were obtained in the spectral region between 50 and 3200 cm⁻¹ for pressures up to 5 GPa. Pronounced changes of the Raman spectra were observed for bands associated to rocking of CO₂⁻; wagging of CO₂⁻; deformations of CO₂⁻, CH₃, and NH₃⁺; and stretching vibrations of SC, CC, CH, CH₂, and CH₃. Upon decompression to ambient pressure the original Raman spectrum prior to compression is recovered. These modifications were associated to a reversible phase transition undergone by the L ‐methionine crystal at about 2.2 GPa, with a hysteresis of ∼0.8 GPa. Pressure coefficients for most of the internal modes of the crystal are given. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman and IR study of high-pressure atomic phase of nitrogen

Atomic phase of nitrogen has been studied up to pressure 250 GPa and temperature 3300 K using a shear diamond anvil cell. This phase was synthesized both from azide NaN₃ and molecular N₂. The atomic phase has been interpreted as a cubic gauche (CG) structure by means of Raman and IR absorption spectroscopy procedures. The phase transition to CG begins at pressure 50 GPa and room temperature for NaN₃ and at 127 GPa for N₂. Observed pressure dependencies and degeneration of phonon modes, the selection rules for IR and Raman spectra, as well equilibrium pressure between molecular N₂ and atomic phase of nitrogen agree well with theoretical predictions for CG.     

On the thermodynamics of phase transitions in metal hydrides

Metal hydrides are solutions of hydrogen in a metal, where phase transitions may occur depending on temperature, pressure etc. We apply Le Chatelier’s principle of thermodynamics to a particular phase transition in TiH _x , which can approximately be described as a second-order phase transition. We show that the fluctuations of the order parameter correspond to fluctuations both of the density of H⁺ ions and of the distance between adjacent H⁺ ions. Moreover, as the system approaches the transition and the correlation radius increases, we show -with the help of statistical mechanics-that the statistical weight of modes involving a large number of H⁺ ions (‘collective modes’) increases sharply, in spite of the fact that the Boltzmann factor of each collective mode is exponentially small. As a result, the interaction of the H⁺ ions with collective modes makes a tiny suprathermal fraction of the H⁺ population appear. Our results hold for similar transitions in metal deuterides, too. A violation of an -insofar undisputed-upper bound on hydrogen loading follows.     

High-pressure Raman spectra of L-isoleucine crystals

Raman spectroscopy investigations of L-isoleucine crystals under high pressures have been carried out up to 7.3 GPa. From this study it was possible to observe modifications on bands associated to both rocking vibrations of r(NH₃⁺) and r(CO₂⁻) as well as to lattice modes at about 2.3 and 5.0 GPa. These modifications were correlated to either conformational change of molecules or to a solid–solid phase transition undergone by the crystals involving the hydrogen bonds that maintain the molecules held in the unit cell. A comparison with a few results on other amino acid crystals is also given.     

Spectroscopic study ofβ-Ni(OH)2 under pressure

Infrared absorption and Raman study ofβ-Ni(OH)₂ has been carried out up to 25 GPa and 33 GPa, respectively. The frequency ofA _2u internal antisymmetric stretching O-H mode decreases linearly with pressure at a rate of −0.7 cm⁻1/GPa. The FWHM of this mode increases continuously with pressure and reaches a value of ∼ 120 cm⁻¹ around 25 GPa. There was no discernible change observed in the frequency and width of the symmetric stretchingA _1g O-H Raman mode up to 33 GPa. The constancy of the Raman mode is taken as a signature of the repulsion produced by H-H contacts in this material under pressure. Lack of any discontinuity in these modes suggests that there is no phase transition in this material in the measured pressure range.     

Structural and magnetic phase transitions in Pr<Subscript>0.7</Subscript>Ca<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> at high pressures

The crystal structure and Raman spectra of Pr_0.7Ca_0.3MnO₃ manganite at high pressures of up to 30 GPa and the magnetic structure at pressures of up to 1 GPa have been studied. A structural phase transition from the orthorhombic phase of the Pnma symmetry to the high-pressure orthorhombic phase of the Imma symmetry has been observed at P ∼ 15 GPa and room temperature. Anomalies of the pressure dependences of the bending and stretching vibrational modes have been observed in the region of the phase transition. A magnetic phase transition from the initial ferromagnetic ground state (T _C = 120 K) to the A-type antiferromagnetic state (T _N = 140 K) takes place at a relatively low pressure of P = 1 GPa in the low-temperature region. The structural mechanisms of the change of the character of the magnetic ordering have been discussed.     

Effect of pressure on Raman spectra of SnS2 single crystals

The 2H polytype of a SnS₂ layered crystal has been studied using Raman spectroscopy at pressures of up to 5 GPa in a diamond anvil cell. The Raman frequency of the intralayer mode increases linearly with increasing pressure at baric coefficients of 5.2 cm⁻¹/GPa for P<3 GPa and 3.4 cm⁻¹/GPa for P>3 GPa. This change in the baric coefficient for Raman scattering and the available data on X-ray measurements of the compressibility of 2H-SnS₂up to 10 GPa suggest that the crystal structure undergoes a transformation at about 3 GPa.