High pressure study of the 2D polymeric phase of C60 by means of raman spectroscopy

Abstract

The effect of high hydrostatic pressure, up to 12GPa, on the intramolecular phonon frequencies and the material stability of the two-dimensional tetragonal Cm polymer has been studied by means of Raman spectroscopy in the spectral range of the radial intramolecular modes (200-800cm^?1). A number of new Raman modes appear in the spectrum for pressures ～ 1.4 and ～ 5.0 GPa. The pressure coefficients for the majority of the phonon modes exhibit changes to lower values at P=4.0 GPa, which may be related to a structural modification of the 2D polymer to a more isotropic phase. The peculiarities observed in the Raman spectra are reversible and the material is stable in the pressure region investigated.     

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.     

The superconducting and the electrical properties of single crystals Bi2Sr2CuCa2oXat high pressure

Abstract

We have investigated the effect of pressure on lattice parameters and Raman-active phonons of the molecular crystal xenon difluride by powder x-ray diffraction and first-order Raman scattering, respectively. The ambient pressure tetragonal crystal structure remains stable up to the maximum pressure of 50 GPa. The compressibility is found to be strongly anisotropic. The frequencies of the intramolecular A1_g stretching mode and the E_g libration increase sublinearly under pressure. ding the a-and c-axis compression data, we have determined the dependence of phonon frequencies on lattice parameters. The high-frequency A1_g mode shows a pronounced nonlinear scaling with c-axis lattice parameter, with particularly small changes during initial compression. This effect is attributed to the interplay between intra-and intermolecular interactions during compression     

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.     

Vibrational spectra of a GaS single crystal

The Raman and infrared active long wavelength phonons of a GaS single crystal were studied at different temperatures in the 10–600 cm^?1 range. Properly polarized Raman spectra could be obtained with the 4880 Å exciting line and the previous assignment of the E_1g modes controversed recently could be confirmed. Infrared spectra were recorded in the 30–600 cm^?1 region. The vibrational frequencies of the crystal were also calculated using a method developed by Wieting and six new frequencies corresponding to infrared and Raman inactive modes have been proposed.We have observed that the degree of leakage of scattered intensity in unallowed polarizations increases when the wavelength of the exciting line moves off the exciton absorption front. The phonon at 74 cm^?1 was particularly sensitive and the question of the antiresonant behaviour of this compound is raised.     

Optical and electrical properties of GaN: Si-based microstructures with a wide range of doping levels

The optical and electrical properties of silicon-doped epitaxial gallium nitride layers grown on sapphire have been studied. The studies have been performed over a wide range of silicon concentrations on each side of the Mott transition. The critical concentrations of Si atoms corresponding to the formation of an impurity band in gallium nitride (～2.5 × 10¹⁸ cm^?3) and to the overlap of the impurity band with the conduction band (～2 × 10¹⁹ cm^?3) have been refined. The maximum of the photoluminescence spectrum shifts nonmonotonically with increasing doping level. This shift is determined by two factors: (1) an increase in the exchange interaction leading to a decrease in the energy gap width and (2) a change in the radiation mechanism as the donor concentration increases. The temperature dependence of the exciton luminescence with participating optical phonons has been studied. The energies of phonon-plasmon modes in GaN: Si layers with different silicon concentrations have been measured using Raman spectroscopy.     

Growth and annealing study of hydrogen-doped single diamond crystals under high pressure and high temperature

A series of diamond crystals doped with hydrogen is successfully synthesized using LiH as the hydrogen source in a catalyst-carbon system at a pressure of 6.0 GPa and temperature ranging from 1255 C to 1350 C.It is shown that the high temperature plays a key role in the incorporation of hydrogen atoms during diamond crystallization.Fourier transform infrared micro-spectroscopy reveals that most of the hydrogen atoms in the synthesized diamond are incorporated into the crystal structure as sp 3-CH 2-symmetric(2850 cm-1) and sp 3 CH 2-antisymmetric vibrations(2920 cm-1).The intensities of these peaks increase gradually with an increase in the content of the hydrogen source in the catalyst.The incorporation of hydrogen impurity leads to a significant shift towards higher frequencies of the Raman peak from 1332.06 cm-1 to 1333.05 cm-1 and gives rise to some compressive stress in the diamond crystal lattice.Furthermore,hydrogen to carbon bonds are evident in the annealed diamond,indicating that the bonds that remain throughout the annealing process and the vibration frequencies centred at 2850 and 2920 cm-1 have no observable shift.Therefore,we suggest that the sp 3 C-H bond is rather stable in diamond crystals.     

Brillouin scattering study of methanol at high pressure

Abstract

Brillouin scattering has been used to study methanol as a function of pressure up to 8.4 GPa. Our near-forward-scattering experiments yield the pressure dependence of the velocity of longitudinal acoustic (LA) phonons, while we determine the pressure dependence of the product of the index of refraction and the LA phonon velocity from our backscattering experiments. The pressure dependence of the LA phonon lifetimes is obtained from the linewidth of the measured Brillouin peaks. From our backscattering experiments we find that the normalized phonon attenuation is a decreasing function of pressure.     

Infrared Spectra of Crystalline,Glassy and Liquid Methanol at High Pressures

Abstract

Mid-infrared spectra in the range 400–1800 cm^?1 of methanol samples in diamond anvil cells at ambient temperature and pressures up to 11 GPa are reported. The freezing pressure is confirmed to be 3.6 GPa, and the spectra of the resulting metastable glass are very similar to those of the liquid. When maintained at high pressure, the glass spontaneously transforms to an ordered crystalline phase which is stable over the range 3.6 to 11 GPa. Small changes in peak wavenumbers for 14 internal modes as a function of pressure are observed, indicating that distortion of the molecules is minimal. A slight decrease for the C-O-H bending mode is attributed to charge transfer from the molecular 0-H bond to the strengthening intermolecular hydrogen bond.     

Far Infrared Spectroscopic Studies of Acetonitrile Vapour

Abstract

The infrared spectrum of acetonitrile vapour has been obtained in the range below 100 cm^?1. There is an absorption band located at 78 cm^?1 which is assigned to overlapping intermolecular vibrations of dimer molecules in equilibrium with the monomer species. The equilibrium constant calculated from the pressure dependence of the band intensity amounts to 42 ± 26 1·mol^?1.     

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.     

Wave-vector dependence of electron-optical phonon coupling in GaAs

Induced non equilibrium distribution of optical phonons allows direct measurement of electron-phonon coupling as a function of phonon wave-vector K. Results indicate that near K=0(K<20, 000 cm^?1 coupling between TO phonons and electrons is independent of K whereas LO phonons show a K^-2 dependence. Results also suggest that electron relaxation in the conduction band by multiple phonon production is quite significant.     

Effect of pressure on the temperature dependence of the thermal conductivity of InSb

The dependence of the thermal conductivity of indium antimonide on temperature (in the range 300–450 K) and hydrostatic pressure (up to 0.4 GPa) has been investigated. It is shown that the phonon thermal conductivity λ_ph obeys the law T ^?n (n ≥ 1). Hydrostatic pressure affects the magnitude and temperature dependence of the thermal conductivity of InSb: with an increase in pressure, the thermal conductivity increases, while the parameter n in the dependence λ_ph ≈ T ^?n decreases.     

Low temperature thermal conductivity of OH− and OD−-doped LIF single crystals

Thermal conductivity measurements between 0.1 and 70K of OH^? and OD^? doped LiF indicates resonant phonon scattering at 0.86cm^? for OH^? and 0.43cm^? for OD^?. Hydroxyl impurities trapped at divalent impurity sites do not scatter phonons resonantly and it is shown that inhomogenous distribution of strong scattering centers modify thermal conductivity curves considerably. A simple tunneling model for the isotope shift suggests an effect similar to the “polaron” model of paraelastic centers. A relaxation time for phonon scattering by OH^? is derived, showing that the ground state may be understood in terms of a direct process, underlining that this system provides a connection between the theory of paraelectric/paraelastic impurities and Jahn-Teller systems.     

Light scattering by electrons in osmium: Effect of pressure

The inelastic electron scattering of light and phonons in single crystals of 5d osmium transition metal has been analyzed at pressures up to 60 GPa and temperatures of 10–300 K. An anomalous increase in the intensity of the spectra of the electron scattering of light with the appearance of pronounced continua at ～580 and 350 cm^?1 for q ‖ [0001] and q ‖ [10\(\overline 1 \)0], respectively, has been observed in a pressure range of 20–30 GPa at an excitation energy of 2.41 eV. The comparison of the q dependences measured and calculated in the framework of the band theory of the spectra implies the significant renormalization of energies and relaxation of electronic states near the Fermi energy and the dependence of the Fermi energy on the pressure and temperature.     

Phonon anomalies and structural transition in spin ice Dy2Ti2O7: a simultaneous pressure‐dependent and temperature‐dependent Raman study

We revisit the assignment of Raman phonons of rare‐earth titanates by performing Raman measurements on single crystals of O¹⁸ isotope‐rich spin ice and nonmagnetic pyrochlores and compare the results with their O¹⁶ counterparts. We show that the low‐wavenumber Raman modes below 250 cm⁻¹ are not due to oxygen vibrations. A mode near 200 cm⁻¹, commonly assigned as F_2g phonon, which shows highly anomalous temperature dependence, is now assigned to a disorder‐induced Raman active mode involving Ti⁴⁺ vibrations. Moreover, we address here the origin of the ‘new’ Raman mode, observed below T_C ~ 110 K in Dy₂Ti₂O₇, through a simultaneous pressure‐dependent and temperature‐dependent Raman study. Our study confirms the ‘new’ mode to be a phonon mode. We find that dT_C/dP = + 5.9 K/GPa. Temperature dependence of other phonons has also been studied at various pressures up to ~8 GPa. We find that pressure suppresses the anomalous temperature dependence. The role of the inherent vacant sites present in the pyrochlore structure in the anomalous temperature dependence is also discussed. Copyright © 2012 John Wiley & Sons, Ltd.     

Optical investigations of the metal-insulator transition in a low-dimensional organic conductor (EDT-TTF)4[Hg3I8]

The polarized reflectance spectra of single crystals of the low-dimensional organic conductor (EDT-TTF)₄[Hg₃I₈] undergoing a metal-insulator phase transition at a temperature T < 35 K have been presented. The spectral region of the study is 700–6000 cm^?1 (0.087–0.74 eV), and the temperature range is 300–9 K. It has been shown that the reflectance spectra are determined by a system of quasi-free electrons of the upper half-occupied molecular π-orbitals, which form a half-filled metallic band in the crystals. A high anisotropy of the spectra and their temperature dependences have been found. For two polarizations, the quantitative analysis of the spectra at 100 and 25 K has been performed in the framework of the phenomenological Drude model, the effective mass and the width of the initial metallic π-electron band have been deter-mined, and it has been found that the conducting system in the crystals has a quasi-one-dimensional character. As temperature decreases, the spectra demonstrate substantial changes indicating the formation of the energy gap (or pseudogap) in the spectrum of electronic states in the range of ～1500–2500 cm^?1. In the low-frequency region (700–1600 cm^?1), a vibrational structure has been observed, and the most intense feature of the structure (ω = 1340 cm^?1) is caused by the interaction of electrons with intramolecular vibrations of the C=C bonds of the EDT-TTF molecule. For temperatures of 15 and 9 K, the analysis of the spectra has been performed in the framework of the theoretical “phase phonon” model taking into account the interaction of electrons with the intramolecular vibrations. It has been concluded that the metal-insulator transition observed in the reflectance spectra of the crystals is similar to the Peierls dielectric transition that occurs in a system of electrons coupled with the intramolecular vibrations of the molecules forming the crystal.     

Raman spectra of MgB2 at high pressure and topological electronic transition

Raman spectra of MgB₂ ceramic samples were measured as a function of pressure up to 32 GPa at room temperature. The spectrum at normal conditions contains a very broad peak at ∼590 cm⁻¹ related to the E _2g phonon mode. The frequency of this mode exhibits a strong linear dependence in the pressure region from 5 to 18 GPa, whereas, beyond this region, the slope of the pressure-induced frequency shift is reduced by about a factor of two. The pressure dependence of the phonon mode up to ∼5 GPa exhibits a change in the slope, as well as a “hysteresis” effect in the frequency vs. pressure behavior. These singularities in the E _2g mode behavior under pressure support the suggestion that MgB₂ may undergo a pressure-induced topological electronic transition.     

Anomalous phonon intensities in the Raman spectrum of disordered CsMg1−xCoxCl3

The five Raman-active $\text{k}\text{= 0}$ phonons have been measured at low temperatures and for a range of x in the disordered lattice CsMg_1-xCo_xCl₃. While the E_2g^a, E_2g^b, E_2g^c and A_1g modes at 55.0, 132.0, 189.0 and 255.0 cm^?1 for x = 0 exhibit normal one-mode behaviour, the intensity of the E_1g phonon at 127.5 cm^?1 has a most unusual concentration dependence which requires a new theory.