Pressure Response of the Higher Fullerene C 84 Studied by Raman and X-ray Scattering

The pressure behavior of the intramolecular phonon modes of the fullerene C 84 and its structural stability have been studied for the first time by means of Raman spectroscopy and synchrotron X-ray diffraction at high pressure up to ～10 GPa. The volume of the cubic unit cell has been measured as a function of pressure. The experimental data fitted by the Murnaghan equation-of-state (EOS) gave K_{0}=19.5\pm 0.9\,\hbox{GPa} and K_{0}^{\prime}=16.4\pm 0.6 . The pressure coefficients and Grüneisen parameters of the intramolecular phonon modes of C 84 have been determined and compared with those of other fullerenes. The data obtained do not show any phase transition and the pressure behavior of the material is entirely reversible in the pressure region investigated.     

Phonon spectrum of a naphthalene crystal at a high pressure: Influence of shortened distances on the lattice and intramolecular vibrations

The Raman spectra of a naphthalene crystal have been measured at room temperature in the pressure range up to 20 GPa. The pressure shift and Grüneisen parameters for intermolecular and intramolecular phonons have been determined. The maximum rate of the pressure shift for intermolecular phonons is 44 cm^?1/GPa, and the rate of the pressure shift for intramolecular phonons lies in the range from 1 to 11 cm^?1/GPa for different modes. The pressure dependence of the phonon frequencies for direct and inverse pressure variations has a hysteresis in the pressure range from 2.5 to 16.5 GPa. It has been shown that the linear dependence of the intermolecular phonon frequency on the crystal density has a peculiarity, which indicates a possible phase transition at a pressure of 3.5 GPa. The pressure dependence of intramolecular phonons related to the stretching vibrations of hydrogen atoms exhibits features that are characteristic of intermolecular phonons, which is associated with the influence of shortened distances between the hydrogen atoms of the neighboring molecules on the intermolecular interaction potential.     

Dynamics of the BiTeI lattice at high pressures

Raman measurements of the phonon spectrum of BiTeI at pressures of up to 20 GPa have been performed. A decrease in the linewidth of E² vibration by almost a factor of 2 with an increase in the pressure to 3 GPa has been detected. The frequencies of all four Raman active modes increase monotonically with the pressure. These lines are observed in spectra up to ～8 GPa. Sharp change in the spectrum occurs at pressures of 8–9 GPa, indicating a transition to the high-pressure phase, which holds up to 20 GPa. This transition is reversible and hardly has any hysteresis. A sample in the high-pressure phase is single crystal.     

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.     

Energy spectrum and phase transitions in C70 fullerite crystals at high pressure

Measurements have been made of the Raman, optical absorption, and luminescence spectra of single crystals and pellets of the fullerite C₇₀ at T=300 K and at pressures up to 12 GPa. The baric shift dω/dP and the Grüneisen parameters of the Raman-active intramolecular phonon modes have been determined. It has been established that the d ω/dP value for certain phonon modes abruptly changes at pressures of P ₁≈2 GPa and P ₂≈5.5 GPa, as do the half-widths of the Raman lines. These features in the Raman spectrum are associated with phase transitions at high pressure. The baric shifts of the absorption and luminescence edges of C₇₀ crystals have been determined and are −0.12 eV/GPa and −0.11 eV/GPa, respectively, for absorption and luminescence. The baric shift of the absorption edge decreases significantly with increasing pressure and is −0.03 eV/GPa at 10 GPa. These data have been used to determine the deformation potential of the fullerite C₇₀, which is about 2.1±0.1 eV. Zh. éksp. Teor. Fiz. 111, 262–273 (January 1997)     

Phase transitions in hydrofullerene C<Subscript>60</Subscript>H<Subscript>36</Subscript> studied by luminescence and Raman spectroscopy at pressures up to 12 GPa

The effect of hydrostatic pressure on the photoluminescence and Raman spectra of hydrofullerene C₆₀H₃₆ was investigated for pressures up to 12 GPa at room temperature. The samples were synthesized by means of high-pressure hydrogenation. The pressure coefficients of the phonon modes were found to be positive and demonstrate singularities at ～0.7 and ～6 GPa. The pressure shift of the luminescence spectrum is unusually small and increases slightly at P≥6 GPa. All observed features are reversible with pressure, and C₆₀H₃₆ is stable in the pressure region investigated.     

Pressure Effects in Phonon Modes and Structure of A II B 2 III C 4 IV Compounds and Combinations

A II B 2 III C 4 VI compounds have been prepared with A II =Zn, Cd, Mn, B III =In, and C VI =S, Se. These atomic substitutions induce modifications in the structure and frequency for some of the phonons. These compounds have been studied by Raman spectroscopy at ambient conditions and under hydrostatic pressures. All phonons appear in the spectral region below 400 cm m 1 . High-pressure measurements have shown the existence of soft modes. New modes seem to appear at high pressures due to the phonon splitting. All low frequency phonons of the Zn 0.6 Mn 0.4 In 2 S 4 compound show a sudden modification in the frequency dependence on pressure above ～2 GPa. Based on the Raman results we propose an assignment for the modes and try to extract information about the structure and the possible phase transitions.     

Pressure-induced transformations and optical properties of the two-dimensional tetragonal polymer of C60 at pressures up to 30 GPa

The Raman spectra of the two-dimensional tetragonal (2D(T)) polymeric phase of C₆₀ have been studied in situ at pressures up to 30 GPa and room temperature. The pressure dependence of the phonon modes shows an irreversible transformation of the material near 20 GPa into a new phase, most probably associated with the covalent bonding between the 2D polymeric sheets. The Raman spectrum of the high-pressure phase is intense and well resolved, and the majority of modes are related to the fullerene molecular cage. The sample recovered at ambient conditions is in a metastable phase and transforms violently under laser irradiation: the transformed material contains mainly dimers and monomers of C₆₀ and small inclusions of the diamond-like carbon phase. The photoluminescence spectra of the 2D(T) polymer of C₆₀ were measured at room temperature and pressure up to 4 GPa. The intensity distribution and the pressure-induced shift of the photoluminescence spectrum drastically differ from those of the C₆₀ monomer. The deformation potential and the Grüneisen parameters of the 2D(T) polymeric phase of C₆₀ have been determined and compared with those of the pristine material.     

First-principles study on superconductivity of solid oxygen

The superconductivity of solid oxygen in ζ phase was investigated by first-principles calculations based on the density functional theory. Using a monoclinic C2/m structure, we calculated the superconducting transition temperature by the Allen–Dynes formula and obtained 2.4 K at 100 GPa for the effective screened Coulomb repulsion constant μ* of 0.13. The transition temperature slowly decreases with increasing pressure and becomes 1.3 K at 200 GPa. The phonon analysis shows that the electron–phonon coupling is dominantly enhanced by the intermolecular vibrations of O₂ rather than the intramolecular ones. The phonon modes showing the strong electron–phonon coupling were found to be concentrated in the phonon frequency range of 100–150 cm^?1 at around the M-point in the Brillouin zone.     

Pressure dependence of zone-boundary phonons in AlSb

Abstract

We have investigated the effect of hydrostatic pressure on zone-boundary and other critical-point phonon frequencies of AlSb by second-order Raman scattering. A softening of the TA(X), TA(L) and (L/T)A([Sgrave]) modes has been observed for pressures up to the first phase transition at 7.7 GPa. The LA(L) as well as the optical TO at X-, L-, and LO at [Sgrave]-, X-points harden with increasing pressure. Mode Griineisen parameters of all the resolved modes were calculated. Reflectivity measurements indicate that the high pressure phase above 7.7 GPa is metallic.     

High pressure raman study of Bi-2212

The hydrostatic pressure dependence of the Raman spectra of Bi₂Sr₂CaCu₂O₈ single crystals has been investigated. The energy of the A _g and B _1g modes was found to increase with pressure in agreement with previously reported measurements, except the strong mode at ～465 cm^?1, which softens with pressure, while another peak at ～458 cm^?1 appears more pronounced at low temperatures and high pressures. The energy of both modes does not seem to change with increasing pressure, up to ～5 GPa, although the average energy of the wide band has been found to soften, which is in disagreement with previously published results. Based on the modifications observed in some phonons at ～1.8 GPa, which correlate with the reduction of T _c and the deformations of the CuO₅ pyramids, we attribute the mode at ～465 cm^?1 to the vibrations of the apex oxygen atoms. All modes due to the oxygen atoms were found to be strongly anharmonic.     

High-pressure Raman study of SnGeS3

Abstract

We report Raman-scattering studies of SnGeS₃ under hydrostatic pressures up to 19.5 GPa. An assignment to internal-external modes is proposed, based on the pressure slopes obtained. Our data show evidence for two critical pressures, one around 7 GPa and a second one around 12 GPa. The material renders itself Raman inactive at 19.5 GPa. The observed changes are reversible upon pressure release.     

Pressure and temperature-dependent raman study of ZnWO4

Abstract

The Raman spectra of monoclinic ZnWO₄ (c⁴ _2h-space group) are reported over wide ranges of pressure (0-24GPa) and temperature (13-970 K). All 18 Raman active pho-nons are observed throughout these ranges. Combining the pressure and temperature Raman data, an identification scheme is suggested which makes possible to distinguish the internal modes (vibrations in the octahedral WO₆ units) from the external ones (pure lattice modes). All phonons harden with pressure, thus showing normal positive dω/dP slopes, and soften with temperature in the region 250 - 970 K (normal negative dω/dT slopes). However, two phonons show a change of slope sign below 300 K, resulting in small positive slopes at low temperatures. Since the pressure dependence of these two phonons is normal and linear, it is concluded that their anomalous, non-linear dependence with temperature is due to anharmonic (temperature induced) phonon interactions rather that volume expansion. It is found that ZnWO₄ remains stable throughout the pressure and temperature ranges.     

Free and bound excitons in silver bromide under hydrostatic pressure

Abstract

Employing resonant Raman and luminescence spectroscopy, various exciton states and phonon modes are studied at low temperature in AgBr under hydrostatic pressure up to 0.7 GPa. The deformation potential for the indirect free exciton gap and mode Grüneisen parameters for various phonons are determined. Excitons bound to neutral donors and isoelectronic iodine are found to essentially derive from L-point valence band states.     

Nanocrystals of cdte formed by the pressure cycle method

Recently, it has been shown that CdTe has two sucessive phase transitions over a narrow pressure range at ?3.5 GPa. In this work, the pressure cycle method using a Paris-Edinburgh cell up to 6 GPa has been applied to CdTe samples in order to obtain recovered CdTe nanocrystals which were characterized by high resolution transmission electron microscopy (HRTEM), electron diffraction and Raman scattering. Such retrieved nanocrystals are nearly spherical, with diameters ranging from 10 to 30 nm, and their structure is zinc-blende (ZB). Their Raman spectra is consistent with the CdTe phonon dispersion curves but reveal a phonon confinement effect.     

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.     

High–pressure electrical conductivity and Raman spectroscopy of chalcanthite

Abstract

The phase transitions and dehydration of chalcanthite were investigated by electrical conductivity and Raman spectroscopy at 1.0–24.0?GPa and 293–673?K in a diamond anvil cell. At ambient temperature, two secondary phase transitions were observed according to discontinuous changes in the slope of Raman shifts, full width at half maximum and electrical conductivities at ～7.3 and ～10.3?GPa. The dehydration temperatures were determined by the splitting of Raman peaks and changes in electrical conductivity as ～350 and ～500?K at respective ～3.0 and ～6.0?GPa. A positive relationship for chalcanthite between dehydration temperature and pressure is established.     

High pressure Raman studies on solid iodine

Abstract

Raman spectra of solid iodine were measured up to 27 GPa. Additional bands, whch appear above 10 GPa, are discussed with respect to a quasi one dimensional molecular phase existing at intermediate pressures and may indicate a more subtle way of molecular dissociation than previously suggested. Higher order spectra due to two-and three phonon processes involving internal and external modes were observed up to 10 GPa.     

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.     

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.