Phase transitions in RbCaF3. I: Optical studies

Phase transitions in RbCaF₃ have been investigated by optical birefringence measurements and Raman scattering experiments. A near discontinuity in the onset of spontaneous birefringence at 196 K shows that the cubic to tetragonal phase change is “slightly” first order. The Raman spectra of the tetragonal phase support a D¹⁸_4h structure in which two phonons of A_1g and E_g symmetry soften as the 196 K transition is approached from lower temperatures. A very slow transition to a lower symmetry structure was observed at about 42 K in the Raman measurements.     

Lattice vibrations of α′-NaV2O5

We have measured far infrared reflectance and transmittance spectra as well as Raman scattering spectra of α′-NaV₂O₅ single crystals for all the principal polarizations. The temperature range above the phase transition temperature T _c =35 K was investigated, mainly. On the basis of this experimental study and of the lattice dynamics calculations we conclude that the symmetry of NaV₂O₅ in the high-temperature phase is described by the centrosymmetric D _2h ¹³ space group. This conclusion leads to important physical consequences concerning the interpretation of one-dimensional magnetic properties of NaV₂O₅ and of the phase transition at 35 K considered earlier to be an ordinary spin-Peierls transition. The assignment of the observed phonons is given. Values of dielectric constants are obtained from the infrared data. Asymmetric shapes of several infrared lines and higher-order infrared vibrational spectra are discussed. The crystal field energy levels of the 3d electron localized at the V⁴⁺ site have been calculated in the framework of the exchange charge model using the values of effective charges obtained from the lattice dynamics calculations. According to the results of these calculations, the broad optical bands observed earlier in the vinicity of 1 eV can be interpreted as phonon assisted d-d transitions. Zh. éksp. Teor. Fiz. 115, 2170–2189 (June 1999) Published in English in the original Russian journal. Reproduced here with stylistic changes by the Translation Editor     

Magnetic-field induced coupling of quasi-degenerate phonon modes in the rare-earth compounds TmVO4 and TbF3

In this work the effects of magnetoelastic interaction in Rare-Earth compounds between excited crystal field states and nondegenerate optical phonons have been studied in tetragonal TmVO₄ and in orthorhombic TbF₃, using Raman and far-infrared spectroscopy. In certain favourable cases a mutual energy renormalization of the phonons has been observed as a function of a magnetic field (TmVO₄) or depending on the direction of the spontaneous magnetization of the crystal (TbF₃).In magnetically ordered TbF₃ an effective phonon-phonon coupling between modes of pure transverse and longitudinal polarization has been studied. This interaction results in an elliptical polarization of the coupled polar modes and transfers transition intensity to the quasi-longitudinal modes.The observed phenomena have been treated theoretically in full agreement with the experiments as higher order effects using the well established theory of magnetoelastic effects.     

Molecular Structures of H2X and D2X(X=0, S,Se, Te)

There are two possible configurations for H₂O, linear(D_∞h) or bent(C_2v). For a C_2v′, the three bands ν_1′ ν₂ and ν₃ should appear in both Raman and infrared. For a D_∞h. however, the ν₁, band should appear in only Raman and the ν₂ and ν₃ bands, in only infrared, that is, a principle of mutual exclusion of Raman and infrared should hold. The present author concludes that H₂X and D₂X(X=O, S, Se, Te) have a linear D_∞h. structure, since the obtained spectra show mutual exclusion of Raman and infrared.     

Crystal fields in PrB6 and NdB6

The electron-phonon relaxation times of the crystal-field levels of the metastable state⁵D₄ of Tb³⁺ were measured between 2 and 4.2K. The relaxation of the lowest pseudodoublet (E=1.25 cm^–1) shows an Orbach process via higher crystal-field levels. The other levels show direct relaxation on a nanosecond time scale. The higher crystal-field levels were used to look for propagation of high-energy (4THz) nonequilibrium phonons by phonon-induced fluorescence. No ballistic propagation of high-energy phonons could be found.     

4f-electron-phonon coupling and lattice dynamics in the ferromagnet LiTbF4

The polarized Raman spectra of LiTbF₄ have been investigated at several temperaturesT150 K, and the temperature dependence of the selfenergies of optical phonons due to the magnetoelastic interaction have been determined. The sizes of these temperature shifts, of the magnetic phonon splittings and of the level repellings between resonant optical phonons and crystal field states have been calculated using the theory of magnetoelastic interaction by Fulde and Thalmeier without any adjustable parameters, considering the modulation of the crystalline electric field by the optical phonons. The phonon modes of LiTbF₄ have been determined in a rigid-ion approximation. Reasonable to good agreement with the experimental results has been obtained for most of the phonon modes.     

Phonons and electronic transitions in the Raman spectra of FeCl2·2H2O and isomorphic compounds

The Raman spectra in FeCl₂ · 2H₂O (FC2) and the isomorphic compounds FeCl₂ · 2D₂O (FC2D), MnCl₂ · 2H₂O (MC2) and CoCl₂ · 2H₂O (CC2) were observed at 2 K to obtain the frequencies of all 12 optical phonons of even symmetry at the zone center. The lowest of these phonons is known to be coupled resonantly to the magnons below T_N. This coupling and other important magnetic properties of the iron salts are determined by the influence of the crystal field. The electronic transitions of the Fe²⁺-ion in a crystal field are identified after a thorough assignment of the phonon lines in the four isomorphic compounds to symmetry types, using back-scattering and 90°-scattering techniques.     

Doping and temperature dependence of inversion symmetry breaking in La2−xSrxCuO4

The doping dependence of the Raman spectra of high quality La_2−xSr_xCu^16,18O₄ polycrystalline compounds has been investigated at low temperatures. It is shown that symmetry forbidden bands peaked at ∼150 cm⁻¹, ∼280 cm⁻¹, and ∼370 cm⁻¹ are activated in the (xx/yy) polarization Raman spectra due to the local breaking of the inversion symmetry mainly at low temperatures and for doping concentrations for which the compound is superconducting. The apparent A₁-character of the activated modes in the symmetry reduced phase indicates a reduction from the D_2h to C_2v or D₂ crystal symmetries, which associates the observed modes to specific IR-active phonons with eigenvectors mainly along the c-axis. The temperature and doping dependence of this inversion symmetry breaking and the superconducting transition temperature are very similar, though the symmetry reduction occurs at significantly higher temperatures.     

Phonon spectra and lattice dynamics of lithium nitride

Lithium nitride, Li₃N, belongs to the hexagonal structure with the symmetry point group D_6h. The structure is ionic with four atoms per unit cell and N^3- coordinated in a regular way with eight Li⁺ ions. Polarized Raman scattering and infrared reflectivity spectra are reported. The frequencies of zone center phonons are determined from a Kramers-Kronig analysis and the oscillator fits to the reflectivity data. A rigid shell model with eight parameters, including the anisotropic polarizability of nitrogen ions, yields an excellent fit to the observed phonon frequencies.     

Raman scattering investigation of ferroelastic Sb5O7I crystals

Sb₅O₇I undergoes a displacive phase transition at 481 K where the symmetry is changed fromC _6h ² toC _2h ⁵ . In the low temperature monoclinic phase the crystal is ferroelastic. The polarized Raman spectra of Sb₅O₇I have been measured at various temperatures below and above the phase transition. The frequencies and symmetries of most of the theoretically expected Raman active phonons in the ferroelastic phase have been determined. The observation of a soft mode in the ferroelastic phase which disappears above the phase transition together with the fact that the unit cell of the ferroelastic phase is twice as large as that of the paraelastic structure permits the conclusion that the phase transition results from a phonon instability at the Brillouin zone boundaryM-point of the hexagonal phase. The temperature dependent splittings and intensity changes of several Raman lines are discussed with respect to the ferroelastic property of the crystal and the phase transition.     

Withdrawal of Electrodynamical Forbiddance and Peculiarities of the SERS Spectra in Fullerene C<Subscript>70</Subscript>

It is demonstrated that in fullerene C₇₀, which can be considered as a deformed fullerene C₆₀ in some mean sense there is a withdrawal of an Electrodynamical forbiddance of a strong quadrupole light-molecule interaction, which is realized in the fullerene C₆₀. This situation occurs because of the reduction of symmetry of C₆₀ from the icosahedral symmetry group Y_h to the group D_5h. The withdrawal results in appearance of the lines in the SERS spectra of C₆₀, which are forbidden in usual Raman scattering and are active in the infrared absorption spectra. The experimentally measured SERS spectra of C₇₀ demonstrates existence of such lines that strongly confirms our ideas about the dipole-quadrupole SERS mechanism.     

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.     

Resonant coupling of optical phonons to J-multiplet excitations in intermediate valent Sm0.75Y0.25S

An anomalous splitting of theJ=0J=1 multiplet transition has been observed by magnetic neutron scattering from intermediate valent Sm_0.75Y_0.25S. The splitting is discussed in terms of a resonant coupling of optical phonons to the magnetic exciton built from the localizedJ=0J=1 multiplet transition by magnetic intersite coupling.     

2 + 1 Flavors QCD Equation of State in NJL Model with Proper Time Regularization

Totally symmetric A_1g phonons are studied for the equilibrium and coherent states of a Bi₂Te₃ lattice. Equilibrium phonons were investigated in the frequency domain by the method of spontaneous Raman scattering, whereas coherent phonons were studied by the method of active femtosecond spectroscopy in the time domain. In the latter case, femtosecond laser pulses were used both for generating and detecting coherent A_1g phonons having a well-defined phase allowing the selective optical control of the lattice dynamics. A comparison of the results obtained in the frequency and time domains suggests that diagonal and nondiagonal elements of the density matrix of lattice excitations relax with the same characteristic time to the equilibrium and zero values, respectively.     

Nonadiabatic interaction of acoustic phonons with spins <Emphasis Type="Italic">S</Emphasis>=1/2 in the two-dimensional Heisenberg model

The ground state of a two-dimensional antiferromagnet having spins S=1/2 and interacting with acoustic phonons is investigated in the nonadiabatic approximation using the quantum-mechanical Monte Carlo method. The critical parameters of the spin-phonon coupling, corresponding to the formation of bound spin-phonon excitations, crystal symmetry lowering, and the emergence of a gap in the spin excitation spectrum, as well as the antiferromagnet-quantum spin liquid transition, are determined. The orthorhombicity parameter, the sublattice magnetization, the violation of the spherical symmetry of spin-spin correlation functions, and the magnetic moment in Gd₂CuO₄ and Eu₂CuO₄ are calculated.     

Lattice dynamics and praphase in N-bensylanyline crystals

N-benzylanyline single crystals are grown, and X-ray diffraction probing of their structure allows their symmetry to be attributed to the C_2h.⁵ phase. Polarized Raman studies of these crystals allow the frequencies of lattice phonons to be estimated and their symmetry to be established. The abnormal behavior of the two lowest-frequency A_g symmetry soft modes, the condensation of which is not detected below the melting point (36–38°C), is noted. The possibility of a high-temperature virtual phase transition and praphase is discussed. Theory group consideration of the praphase allows determination of its symmetry and the symmetry of phonons related to the virtual phase transition.     

Effect of deuteration on the electronic and electron-vibrational properties of the organic conductor k-(D8-BEDT-TTF)2[Hg(SCN)2Br]

We present here for the first time polarized reflection spectra and optical conductivity spectra of single crystals of the newly deuterated organic conductor k-(D₈-BEDT-TTF)₂[Hg(SCN)₂Br] at room temperature. The spectral region investigated is 700–40 000 cm⁻¹. We examined the effect of deuteration on electronic and electron-vibrational transitions observed in the spectra. The observed shift of the electron “dimer” transition in the infrared toward lower frequencies upon deuteration is linked with an increase in the interaction between neighboring, mutually perpendicular dimers in the structure of the deuterated crystal. A lowering of the symmetry of the BEDT-TTF molecule is demonstrated in crystals similar to k-(BEDT-TTF)₂[Hg(SCN)₂Br], relative to the symmetry D _2h of the free molecule. We refine the assignment of the spectral features determined by the interaction of electrons with the fully-symmetric intramolecular vibrations of the C=C, C-S, and C-C-H bonds of the BEDT-TTF molecule. Fiz. Tverd. Tela (St. Petersburg) 40, 1595–1598 (September 1998)     

Vibrational spectroscopy of tolane; Coriolis coupling between Raman-active modes of g symmetry

ABSTRACT

Vibrational spectroscopy of tolane (diphenylacetylene), which has 66 normal modes, has been advanced. Anharmonic wavenumber predictions were made with the quartic potential energy surface obtained with B3LYP/cc-pVTZ model and the second-order perturbation theory (VPT2). Infrared (IR) intensity and Raman activities were computed at the harmonic level. The IR spectrum of the crystal and Raman spectra of the liquid and the crystal tolane were newly recorded. The lingering problem of an excess of polarised Raman bands at wavenumbers appropriate for fundamentals, other than a_g modes, has now been attributed to Coriolis coupling within modes of g symmetry species. Consequently, D_2h point symmetry group has been confirmed for a planar tolane molecule. Assignments for almost all fundamentals of tolane are now secure. The assignment for ν₃₂ remains questionable. Remaining unassigned fundamentals are: ν₃₄ and ν₃₅, which, as a_u symmetry species, are IR- and Raman-inactive transitions, and ν₅₉(b_2u), which is predicted to have a very low wavenumber.     

Spectral studies of Nd3+ and Er3+ ions in POCl3:SnCl4 laser liquid

The optical absorption spectra of triply ionized neodymium and erbium ions in POCl₃SnCl₄ laser liquid have been studied for the first time in the UV-VIS and NIR regions. Spectroscopic and Judd-Ofelt intensity parameters are evaluated from the observed band positions and their intensities. Radiative lifetimes and the luminescent branching ratios for the excited fluorescent levels of Nd³⁺ and Er³⁺ ions are theoretically estimated and the possible laser transitions are indicated. From the observed splittings of certain bands in the second-derivative spectrum of the Nd³⁺ ion, the crystal field (A ₂₀,A ₄₀) parameters are evaluated assumingC _3h symmetry for the ion.