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.     

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.     

Infrared absorption spectra of a Nd0.5Ho0.5Fe3(BO3)4 crystal

Infrared absorption spectra of a Nd_0.5Ho_0.5Fe₃(BO₃)₄ crystal in the spectral range of 30–1700 cm^–1 have been measured at temperatures from 6 to 300 K. The experimental spectra have been analyzed based on the semiempirical calculation of the lattice dynamics and the analysis of correlation diagrams of borate complexes. No changes associated with structural phase transitions have been detected in the temperature range of measurements; the effect of magnetic ordering on the infrared absorption spectra has not been observed.     

Infrared reflectivity and Raman scattering of lithium oxide single crystals

Infrared reflection and Raman spectra of single crystals of lithium oxide have been measured at room temperature. The reflection spectra have been analyzed by means of a fit with a classical dispersion formula. The result gives the frequencies of the fundamental transverse and longitudinal optical modes as 425 and 737 cm^?1, respectively. The frequency of the Raman active fundamental mode is also established at 523 cm^?1. From these frequencies an effective charge of lithium ion and effective force constants are obtained on the basis of lattice dynamical models.     

Molecular vibrations and lattice dynamics of ortho-terphenyl

Infrared and Raman spectra of crystalline, melted and solvated ortho-terphenyl and its perdeuterated isotopomer, D₁₄-ortho-tephenyl, have been recorded. Optimized geometries and vibrational frequencies were calculated by the semiempirical RHF/AM1 method and by DFT using the B3LYP functional and 6–31G(d) basis set. In both cases the lowest energy conformation is of C₂ symmetry. With the scaled AM1 and B3LYP/6-31G(d) force fields the average error in reproducing the experimental molecular vibrational frequencies is 13cm^?1 and 5cm^?1, respectively. The AM1 potential energy surface for phenyl torsions was mapped on a 15° grid. The barrier to concerted internal rotation is estimated to lie between 3 kJ mol^?1 and 6kJ mol^?1. The calculations of the lattice dynamics at k = 0 in the low temperature fully ordered crystal phase of parent and deuterated ortho-terphenyl were performed with inclusion of six low lying intramolecular vibrations. The conformational change of the ortho-terphenyl molecule induced by crystal packing forces was taken into account by re-defining the unperturbed molecular vibrational state. Although an accurate assignment of lattice vibrations was not possible, the calculated spectra give quite a reasonable picture of the low frequency dynamics in crystalline ortho-terphenyl. The relevance of the results obtained to the glass forming property of ortho-terphenyl is discussed.     

Intramolecular phase phonon absorptions as probes of the donor and acceptor chain contributions to the phase transitions of TTF-TCNQ

Below the metal-insulator transition the infrared absorption spectra (4000-200 cm^-1) of TTF-TCNQ powders display antiresonance dips above the electronic gap and two phase phonon absorptions at 317 and 253 cm^-1 attributable to the interaction of electrons with intramolecular modes of TTF and TCNQ. The temperature dependence of the two absorptions shows that the 54 K metal-insulator transition is driven by the Peierls distortion on the TCNQ sublattice whereas the distortion on the TTF chains increases markedly around the 49 K phase transition.     

Far infrared polarization measurements of MEM(TCNQ)2 at room temperature and 4.2 K

Polarization measurements have been made in the far infrared absorption spectra on single crystals of MEM(TCNQ)₂ at 1.5, 4.2 and 298 K. We demonstrated experimentally that the direction of polarization of phonons at 126 and 156 cm⁻¹ below spin-Peierls transition are parallel to the c-axis. Secondly, we measured the absorption spectra of MEMI powder at 1.5 and 4.2 K and found that there is no absorption in the range from 130 to 170 cm⁻¹. This indicates that there is no intramolecular vibration of MEM in this region. It supports the assignment of 156 cm⁻¹ absorption as phonon. Thirdly, comparing the FIR absorption spectra at 4.2 and 298 K with linearly polarized radiation field parallel to the c-axis, we found that the height of the strong absorption band observed around 86–180 cm⁻¹ region at 4.2 K becomes lower with the raising of temperature to 298 K. We attributed this band to the pinned CDW. The lowest edge of the CDW is 70 cm⁻¹.     

Optical investigations of anisotropy of the conducting π-electron system in crystals of the organic superconductor (EDT-TTF)4[Hg3I8]1 − x

The polarized reflectance spectra of microcrystals of the new organic superconductor (EDT-TTF)₄[Hg₃I₈]_{1 ? x} (T _c = 8.1 K for x = 0.027; T _c = 7 K at 0.3 kbar for x = 0.019) have been investigated in the spectral region of 700–6000 cm^?1 (0.087–0.740 eV) at temperatures ranging from 10 to 300 K. A quantitative analysis of the spectra has been performed in the framework of the phenomenological Drude and Drude-Lorentz dispersion models, as well as in the framework of the theoretical “phase phonon” model that takes into account the interaction of free electrons with intramolecular vibrations. The effective mass of charge carriers m*, the width of the initial metallic π-electron band W, and the integral t of the electron transfer between the molecular π-orbitals of neighboring molecules have been determined. In the low-frequency range (700–1600 cm^?1), the vibrational structure associated with intramolecular vibrations of the EDT-TTF molecule has been revealed. It has been shown that the most intense feature (ω = 1330 cm^?1) of this structure is caused by the interaction of “quasi-free” electrons with intramolecular vibrations.     

新型BCN化合物的结构表征和相转变

将石墨和六方氮化硼(h-BN)混合粉球磨120h形成的非晶B-C-N粉在4.5GPa，1600K等温退火45min. XRD，TEM和Raman散射测量结果表明，高压合成的产物由晶格常数为a₁=0.2551nm，c₁=0.6716nm的六方Ⅰ相和a₂=1.2360nm，c₂=0.8570nm的六方Ⅱ相组成，其中六方Ⅱ相为B-C-N 新相. 在室温该新相在1279，1368，1398cm^-1出现三个特征Raman峰. 变温Raman测量结果表明，在测量温度T=93K时，样品中的主要相为六方Ⅰ相，随着温度的升高，六方Ⅰ相逐渐向六方Ⅱ相转变，当T>473K时，六方Ⅰ相完全转变成六方Ⅱ相. 当温度从673K降到93K过程中，样品又从六方Ⅱ相逐渐变回到六方Ⅰ相. 对这一相变的机理进行了讨论. 关键词： B-C-N 机械球磨 高温高压 相转变     

Raman spectra of single-crystal C60

We have analysed the Raman spectra of C₆₀ single crystals between room temperature and 10K and studied the temperature-induced phase transition in this material. The spectra show crystal field splitting of the internal Raman modes but no evidence for a line shift near the phase transition. The photo-induced transformation of the crystals and its implication on the interpretation of the Raman spectra is discussed. In the low temperature phase we observed two lines at 30 cm^–1 and 41 cm^–1 which we assign to the librational modes of the crystal.     

Infrared Spectroscopy Investigation of Cubic Boron Nitride Films

Abstract

FT-IR Spectroscopy have been used for identifying both the structure of BN and the intensity of the compressive stress in cubic boron nitride (c-BN) film prepared by a unbalanced of (13.56 MHz) magnetron sputtering of a hexagonal boron nitride target in a mixture argon and nitride discharge. A T(temperature) - V(negative bias) phase diagram was obtained using the phase structure identify by IR spectra. Comparing the reflection infrared spectra (RIR) with the transmission infrared spectra (TIR) measured from same c-BN film, it is firstly found that RIR peak position of c-BN is lower than TIR peak position of c-BN, this means that the compressive stress on the surface layer of c-BN film is smaller than that inside c-BN film, may be this is the reason why thicker c-BN film can not be synthesized. A higher IR peak position of 1064 cm^?1 and a lower peak position 1004.7 cm^?1 were detected from a broken and partly peeled off c-BN film. The peak position of 1064 cm^?1 agrees with that of bulk c-BN at 1065 cm^?1 which was synthesized at high temperature and high pressure, while the peak position of 1004.7 cm^?1 accords well with the result calculated (1004 cm^?1) by Wentzcovitch and it may be closes to that of the stress free value of c-BN. Using the result measured by Ulrich, the shift rate of IR peak position of c-BN in the films is about 3.8 cm^?1/Gpa to be obtained.     

BaTiO3和Ce:BaTiO3单晶的高温喇曼散射研究

从室温至180℃测量了BaTiO₃和Ce:BaTiO₃单晶的偏振喇曼谱,在X(ZZ)Y几何配置下发现了三条频率分别为986,1204和1480cm^-1的新谱线.根据喇曼散射截面的温度依赖关系,确认这些新谱线对应二阶喇曼散射,而A₁(TO)谱中位于275和514cm^-1处的非对称宽峰则属于一阶喇曼散射.在此基础上,对立方相BaTiO₃的喇曼谱和结构相变机制进行了讨论.通过比较B     

Fluid synthesis and structure of a new polymorphic modification of boron nitride

A new previously unknown phase of boron nitride with a hardness of 0.41–0.63 GPa has been pre-pared by the supercritical fluid synthesis. The presence of a new phase is confirmed by the X-ray spectra and IR absorption spectra, where new reflections and bands are distinguished. The fundamental reflection of the X-ray diffraction pattern is d = 0.286–0.291 nm, and the characteristic band in the infrared absorption spectrum is observed at 704 cm^?1. The X-ray diffraction pattern and the experimental and theoretical infrared absorption spectra show that a new synthesized boron nitride phase can be a cluster crystal (space group 211) with a simple cubic lattice. Cage clusters of a fullerene-like morphology B₂₄N₂₄ with point symmetry O are arranged in lattice sites.     

Raman scattering from soft to-phonon in IV–VI compound semiconductors

The soft TO-phonon modes were investigated below the cubic-rhombohedral transition temperature in Pb_1?xGe_xTe (x=0.05) and SnTe. We observed resolved Raman spectra from ordinary and extraordinary modes. The temperature dependence of the spectra was analyzed in terms of phonon-phonon interactions. We also discussed origins of extra Raman spectra which appear even in the high temperature phase. The energy gain of valence bonding electrons due to lattice distortions was estimated to be ≈10⁹erg/cm³ by analyzing anomalous temperature behavior of the optical dielectric constant. This is about two order of magnitude larger than the depth of the well of free energy.     

Raman scattering studies on manganese ion-implanted GaN

This paper reports that the Raman spectra have been recorded on the metal-organic chemical vapour deposition epitaxially grown GaN before and after the Mn ions implanted. Several Raman defect modes have emerged from the implanted samples. The structures around 182 cm^-1 modes are attributed to the disorder-activated Raman scattering, whereas the 361 cm^-1 and 660 cm^-1 peaks are assigned to nitrogen vacancy-related defect scattering. One additional peak at 280 cm^-1 is attributed to the vibrational mode of gallium vacancy-related defects and/or to disorder activated Raman scattering. A Raman-scattering study of lattice recovery is also presented by rapid thermal annealing at different temperatures between 700 °C and 1050 °C on Mn implanted GaN epilayers. The behaviour of peak-shape change and full width at half maximum (FWHM) of the A₁(LO) (733 cm^-1) and E^H₂ (566 cm^-1) Raman modes are explained on the basis of implantation-induced lattice damage in GaN epilayers.     

Multiphonon absorption in a MgO single crystal in the terahertz range

The reflection and transmission spectra of a MgO single crystal at frequencies of 10–1000 cm⁻¹ in the temperature range 10–300 K have been measured using submillimeter and infrared Fourier spectros-copy. The evolution of anharmonic absorption with variations in temperature has been investigated in the frequency range below the frequency of the transverse optical phonon. The parameters of the dispersion model that adequately describes the lattice absorption of terahertz radiation in single-crystal magnesium oxide have been determined.     

The pressure effect on the photoluminescence and Raman spectra of Nd(DBM)3·Phen

Photoluminescence and Raman spectra of rare earth complex Nd(DBM)₃·Phen (DBM, dibenzoylmethane; Phen, 1,10-phenanthroline) are measured at high pressures. A new Raman band appearing at 1070 cm⁻¹ indicates a second-order phase transition around 5.0 GPa. Although the crystal lattice is destroyed for pressures higher than 7.1 GPa, photoluminescence spectra show that the emission intensity of Nd³⁺ is enhanced dramatically with the pressure increasing up to 9.9 GPa, which is attributed to an efficient intramolecular energy transfer from the ligand to Nd³⁺. By analyzing the energy of the ground and excited states at 9.9 GPa, the ⁴H_11/2 energy level is considered as the main resonance energy level that efficiently accepts the transferred energy from the ligand.     

Resonance dipole-dipole coupling and Fermi resonance in CF4 dimers

The FTIR spectra of Ar(Ne)/CF₄ matrixes have been recorded at matrix concentrations varying in the range 10 000-600 cm⁻¹. The absorptions due to the CF₄ monomers and to the (CF₄)₂ resonance dimers in the spectra of the two matrixes have been identified. The intramolecular Fermi resonance in the spectra of the CF₄ monomers trapped in solid argon and neon has been analyzed. The spectra of the (CF₄)₂ dimers are determined by the strong resonance dipole-dipole interaction of the two interacting molecules and by strengthening or weakening of the intramolecular Fermi resonance interaction.     

Electronic and electronic-vibrational phenomena in the new organic conductor ϰ-(ET)2[Hg(SCN)2Cl] with a metal-insulator transition

The reflection spectra and optical conductivity spectra of the new organic conductor ϰ-(ET)₂[Hg(SCN)₂Cl] with a metal-insulator transition in the spectral regions 700–5500 and 9000–40 000 cm⁻¹ have been studied in polarized light at 300 K. A comparisonis made between the spectra obtained and the corresponding spectra of related isostructural conductors based on the ET molecule, and also the properties of the crystal structure of the investigated compounds. An electronic transition between the ET molecules of the dimer (ET) ₂ ⁺ in the spectral region 700–5500 cm⁻¹ has been identified, as have the features of the electronic-vibrational structure arising as a consequence of the interaction of this transition with the completely symmetric intramolecular vibrations of the ET molecule. It is found that the conductor with the stronger dimer interaction between the ET molecules has the higher the transition temperature. Fiz. Tverd. Tela (St. Petersburg) 39, 1313–1319 (August 1997)     

Effect of hydrostatic pressure on the Raman spectrum of anatase (TiO2)

Raman spectra of anatase have been investigated under pressures up to 60 kbar and at room temperature. A pressure-induced phase transition is observed at pressures above 25.6 kbar. The 197 cm^-1 mode (at 1 atm.) of six Raman active modes exhibits anomalous pressure dependence in which the frequency decreases with increasing pressure. This mode may be significant in the phase transition. The remaining modes show usual behavior.