A two-fraction model for the calculation of the resonance spectra of the complex permittivity of ice in the far infrared

A two-fraction model that makes it possible to calculate analytically the complex dielectric permittivity of ice in the far infrared and submillimeter wavelength ranges is proposed. The librational and vibrational fractions are considered. The first fraction, consisting of rigid dipoles executing anharmonic reorientations in defects of the structure, gives rise to the librational band of ice at 800 cm^?1. The second fraction consists of elastically vibrating oppositely charged H-bonded molecules. This fraction describes two bands of ice in the range 100–300 cm^?1, and the nonresonant background of dielectric losses in the submillimeter wavelength range. The dielectric permittivity spectra of ice calculated for the temperature of ?7°C are consistent with the experimental spectra. The spectra of ice at the temperature ?30°C are predicted.     

Electrodynamic properties of nanoporous silicon in the range from terahertz to infrared frequencies

The dielectric response (conductivity and permittivity) spectra of a series of nanoporous silicon samples prepared by anodization of low-resistivity single-crystal silicon are measured, for the first time, using terahertz and IR spectroscopy in the frequency range 7–4000 cm^?1 at room temperature. The spectra obtained are analyzed in terms of the effective medium theory with a size-dependent dielectric response function of nanoinclusions and averaged dielectric characteristics of the surrounding medium. The geometric and dielectric characteristics of silicon nanoinclusions are determined. The dielectric properties of inclusions are found to be affected by nanosize effects, namely, carrier scattering at crystallite boundaries and a broadening of the band gap due to quantum confinement. The spectra of the samples prepared by adding iodine to the electrolyte exhibit a resonance at frequencies of 150–300 cm^?1. The nature of the resonance can be associated with the presence of chemisorbed iodine on the surface of porous silicon. Possible mechanisms responsible for the changes in broadband conductivity and permittivity spectra of single-crystal silicon upon transformation into a nanoporous structure are discussed.     

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.     

Oscillator parameters of transverse phonons in <Emphasis Type="Italic">a</Emphasis>-domain lead titanate

The temperature behavior of polarized Raman spectra of a-domain PbTiO₃ single crystals has been investigated. The spectra obtained are fit by a damping harmonic oscillator model with allowance for a complex background structure. A full set of oscillator parameters of all phonon modes in the frequency range 12 < ν < 1200 cm^?1 is obtained and their temperature dependences in the range from 300 to 800 K are presented.     

Infrared spectrum and vibrational potential function of thionylimide (HNSO)

The ir absorption of gaseous HNSO, DNSO and H¹⁵NSO is recorded in the range 300–4100 cm^?1 at medium resolution. Besides the fundamental vibrations, overtones and combination bands are measured and assigned. From these data, combined with the ir absorptions of four more isotopic species of thionylimide, and with the centrifugal distortion constants of HNSO and DNSO, a harmonic force field, with 11 constants was derived.     

Dielectric behaviour of cellulose acetate-based polymer electrolytes

The present work deals with the findings on the dielectric behaviour of cellulose acetate (CA) and its complexes consisting of ammonium tetrafluoroborate (NH₄BF₄) and polyethylene glycol with a molecular weight of 600?g/mol (PEG₆₀₀) that were prepared using the solution casting method. The highest ?? obtained for CA-NH₄BF₄ film was 2.18?×?10^?7 S cm^?1 and enhanced to 1.41?×?10^?5 S cm^?1 with the addition of 30?wt.% PEG₆₀₀. The dielectric behaviours of the selected samples were analyzed using complex impedance Z*, complex admittance A*, complex permittivity ?*, and complex electric modulus M*-based frequency and temperature dependence in the range of 10?Hz?C1?MHz and 303?C363?K, respectively. The variation in dielectric permittivity (?? _r and ?? _i) as a function of frequency at different temperatures exhibits a dispersive behaviour at low frequencies and decays at higher frequencies. The variation in dielectric permittivity as a function of temperature at different frequencies is typical of polar dielectrics in which the orientation of dipoles is facilitated with the rising temperature, and thereby the permittivity is increased. Modulus analysis was also performed to understand the mechanism of electrical transport process, whereas relaxation time was determined from the variation in loss tangent with temperature at different frequencies.     

Polar phonons and specific features of the ferroelectric states in cadmium titanate

Polarized spectra of reflectance R(ν) and transmittance Tr(ν) of single-crystal CdTiO₃ samples have been obtained in the frequency range 7 < ν < 1000 cm^?1 and for temperatures from 5 to 300 K using IR Fourier spectroscopy and submillimeter-range techniques. Dispersion analysis was carried out in terms of the additive-oscillator model, and dielectric responses ε(ν) and ε″(ν) were calculated. The polar modes were assigned to particular symmetry types, and their oscillator parameters (dielectric contributions, normal frequencies, damping constants) were determined. The numerical values of the components of the static permittivity tensor, ε₁₁ and ε₃₃, are shown to be almost fully determined by the total dielectric contributions due to the B_3u and B_1u phonons, respectively. In the low-frequency domain, lines showing anomalous behavior of the oscillator parameters, which is characteristic of soft ferroelectric modes, were observed. It is shown that, in CdTiO₃ at cryogenic temperatures, there exist several different polar states with switching in the direction of the spontaneous polarization vector.     

Vibrational spectrum of Li2B4O7 crystals

Polarized IR reflection spectra of Li₂B₄O₇ crystals are studied in a spectral range of 80–1600 cm^?1 and compared with their Raman spectra. Based on the results of the dispersion analysis of the spectra, the frequencies, damping constants, and oscillator strengths of all vibrations are determined. The inversion of frequencies of the longitudinal and transverse vibrations of the A ₁ and E symmetry in a range of 900–1150 cm^?1 is found. Based on the data thus obtained, the effective charges are calculated and the types of chemical bonds are analyzed for structural groups of the Li₂B₄O₇ crystal.     

Raman spectroscopy of the OH group vibrations in structural complexes of liquid water

A number of spectral features in the structure of the OH band of water located at ～3450 cm^?1 are registered in a series of 34 Raman spectra. Each spectrum of the series is excited by a pair of successive secondharmonic pulses of a moderate intensity (15–20 MW/cm²) from a Nd:YAG laser operating at a pulse repetition frequency of 1 Hz. The pairs of pulses in the series follow at an interval of 15–20 s. It is found that, in ten measurements of the first series, there occur three successively reproduced spectra with an anomalously narrow band (down to 260 cm^?1) and spectra with a local minimum in the range of 3400 cm^?1. The occurrence of the latter spectra was predicted previously as a manifestation of the occurrence of structural fragments of water. In the range 3690–3700 cm^?1, a narrow peak of free OH vibrations is observed, whose intensity decreases in subsequent series. Some Raman spectra are similar to the spectra of the OH vibrations of water clusters in molecular beams and surface layers. These data make it possible to assume that structural complexes exist in the volume of water irradiated by the laser beam, with the lifetime of some of them being no shorter than 40 s.     

Electrodynamic properties of lead Zirconate-Titanate thin films in the terahertz frequency range

The transmission/reflection spectra of bilayer structures consisting of thin amorphous and polycrystalline Pb(Zr_0.52Ti_0.48)O₃ ferroelectric films deposited on dielectric substrates of magnesium oxide MgO and sapphire α-Al₂O₃ were measured in the frequency range of 5–4000 cm^?1. Based on these spectra and using the dispersion analysis method, the spectra of complex dielectric permittivity ?*(ν) and dynamic conductivity σ′(ν) of the films were simulated, the electrodynamic parameters of the films were determined, and the dielectric dispersion responsible for the formation of static permittivity was found.     

Kondo scattering and properties of TmSe in the infrared region

The conductivity and permittivity spectra of the intermediate-valence semiconductor TmSe have been measured by terahertz and infrared spectroscopy in a frequency range of 10–10⁴ cm^?1 and a temperature range of 5–300 K. At low temperatures (5 K < T < 100 K), the spectra contain a gap Δ ≈ 2.5 meV, whose appearance is considered to be related to conduction-electron localization at local magnetic moments. At high temperatures (100 K < T < 300 K), the dielectric response is specified by two electronic components: “ light” conduction electrons and “heavy” hybridized f-d states. The microscopic parameters of both components, such as the concentration, mobility, effective mass, relaxation frequency, and the plasma frequency, are determined.     

Inner vibrational modes and anhar-monicity of Mg-OH− complexes in naf single crystals

Abstract

Different inner vibrational modes (stretching, bending and their combination) of the OH^? ion perturbed by lattice defects induced by Mg²⁺ in NaF have been put in evidence and studied by means of optical absorption spectroscopy in the 600–7200 cm^?1 wavenumber range, in the 9–300K temperature range, and for Mg²⁺ molar concentration ranging between 10^?4 and 10^?3. Electrical and mechanical anharmonicity effects have been detected for the stretching modes and analyzed in the framework of the anharmonic oscillator model for a diatomic molecule.     

Dielectric relaxation of KBr doped with KOH and KOD

The complex dielectric constant of KBr single crystals doped with KOH and with KOD has been measured in the temperature range from 0.32°K to 300°K using a small a. c. signal. A relaxation timeτ ₀ was determined by means of Cole-Cole plots. ForT<4°K the temperature dependence ofτ ₀ can be approximated byAT ^?n , wheren is between 1.2 and 1.3 for the dilute samples, and between 0.8 and 1.0 for two samples with large hydroxyl concentrations.n has the same value for OH^? and OD^? dipoles. The constantA roughly doubles upon substitution ofH byD. The relaxation behavior was found to be independent of concentration in the range between 3×10¹⁸ cm^?3 dipoles and 10¹⁹ dipoles cm^?3.     

Subterahertz electrodynamics of (TMTSF)2X (X = ClO4, PF6) salts

The terahertz-subterahertz spectra of the complex permittivity and dynamic conductivity of polycrystalline (TMTSF)₂ClO₄ and (TMTSF)₂PF₆ samples are measured quantitatively. The spectra of (TMTSF)₂ClO₄ have absorption lines at frequencies of 7 and 30 cm^?1. The obtained temperature dependences of the line parameters in the range 5–300 K cast some doubt on the earlier concept of their phonon origin. An excitation is detected at temperatures below 20 K in the frequency range near 30 cm^?1, and its nature is related to the activation of a transverse acoustic phonon caused by the folding of the Brillouin zone due to the ordering of noncentrosymmetrical anions below 20 K. An increase in the carrier relaxation rate is found in this temperature range, which indicates a close relation between the electron and phonon subsystems in (TMTSF)₂ClO₄. Sings of additional low-energy excitations that should manifest themselves at frequencies below 1–2 cm^?1 are detected. (TMTSF)₂PF₆ containing centrosymmetrical anions has no absorption lines in the frequency range 3–20 cm^?1 and the temperature range 5–300 K.     

Four-photon laser spectroscopy of liquid water and aqueous solutions of α-chymotrypsin in the range ±5 cm<Superscript>−1</Superscript>

The resonances located at 1.2, 1.6, 2.0, and 2.3 cm^?1 with a width of ～0.2 cm^?1 were observed for the first time in the range ±5 cm^?1 of the four-photon Rayleigh wing spectra of distilled water and aqueous solutions of the protein α-chymotrypsin. The line at 2.3 cm^?1 belongs to the rotational transition 3(2, 1)–4(1, 4) of the ground vibrational state of water. In the presence of the protein, the spectrum is modified by the appearance of new lines, located at 0.74, 2.8, and 3.2 cm^?1. The modification of the spectrum observed is interpreted as a manifestation of low-frequency vibrations of large molecular fragments in aqueous protein solutions and as a result of the structuring of water in the vicinity of protein molecules.     

Far-infrared spectrum and dielectric function of KCN and NaCN in the disordered cubic phase

The far-infrared reflection spectrum of KCN and NaCN in their cubic disordered phases is measured between 20 and 400 cm^?1 with dispersive Fourier-spectroscopy and the complex dielectric function ε&#x0302;(ω) is evaluated. At 295 K KCN exhibits a well defined TO mode at 148 cm^?1. The LO mode is at 234 cm^?1. The dielectric function of NaCN between 295 and 363 K is more complicated. Below 150 cm^?1 it can be approximated by an overdamped oscillator at 120 cm^?1.     

Low-frequency librational vibrations,boson peak,and interchain interactions in a vitreous polymer

The IR and Raman spectra of plasticized poly(methyl methacrylate) (PMMA) are measured and analyzed in the frequency range 10–120 cm^?1, in which the absorption and scattering due to the individual (85–90 cm^?1) and correlated librational vibrations (15–20 cm^?1, boson peak) preceding the appearance of relaxation dynamics manifest themselves. It is demonstrated that the presence of the boson peak as an indication of the solid-state behavior of the polymer material in the low-frequency spectra is associated with the correlation of librational vibrations not only inside macromolecules (in segments corresponding in length to the Kuhn segment) but also in segments of neighboring chains.     

High-resolution infrared and laser photoacoustic spectroscopy of monochloroacetylene

High-resolution vibration—rotation spectra of monochloroacetylene (HCCCl) have been recorded in two different wavenumber regions. Fourier transform infrared interferometer measurements in the 4000–10000cm^?1 range have been performed with a resolution of 0.005–0.016cm^?1 and titanium: sapphire ring laser intracavity photoacoustic measurements in the 12500–12600cm^?1 and 12800–12860cm^?1 regions have been carried out with a Doppler-limited resolution of about 0.02 cm^?1. Altogether, 40 vibrational bands belonging to the HCC³⁵ Cl and 15 bands belonging to the HCC³⁷ Cl isotopic species have been rotationally assigned. A vibrational model, based on the conventional rectilinear normal coordinate theory including anharmonic Fermi, Darling—Dennison and vibrational l-type doubling resonances, has been used to attach vibrational labels to the bands. This approach is found to describe well the rovibrational energy level structure at least in the energy range covered in this work. The model shows that the CH oscillator becomes decoupled from the rest of the molecule as vibrational energy increases.     

Low-frequency optical lattice vibrations in Hg<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te alloys

The lattice reflection spectra of the Hg_{1 ? x} Cd _x Te (x = 0.06–0.70) alloys measured in the low-frequency range of optical vibrations (the region of the anomalous mode of Hg-Te vibrations in HgTe) at room temperature are interpreted. The low-frequency modes observed at frequencies of 98, 105, and 112 cm^?1 for all compositions of the Hg_{1 ? x} Cd _x Te alloy are assigned to the modes of Hg-Te vibrations, as was previously done for modes of Cd-Te vibrations in the quasi-molecular approximation. According to the double-well potential model for the Hg atom in the crystal lattice of the alloy, the Hg atom either can occupy the center of the anion tetrahedron or can be located in the off-center position. The fundamental strong mode of Hg-Te vibrations at a frequency of about 120 cm^?1 (at T = 300 K) corresponds to the vibrations of the off-center Hg atom, and the low-frequency vibration modes correspond to the vibrations of the Hg atom located at the center of the anion tetrahedron.