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)     

Polarized absorption spectra of Co2+ in Na2Cd3Cl8 single crystals

Summary The polarized optical absorption spectra of Na₂Cd₃Cl₈: Co²⁺ in the range of 15 000 to 40 000 cm⁻¹ down to 15 K are reported. The Co²⁺ ion is found to occupy the Cd²⁺ sites in octahedral geometry and the spectra are interpreted satisfactorily in terms of a cubic ligand field model including spin-orbit coupling. The observed crystal field spectra are well reproduced withB=745 cm⁻¹,C=3410 cm⁻¹,Dq=700 cm⁻¹ and ζ (spin-orbit interaction) =520 cm⁻¹. No spectral evidence for tetragonal distortion is observed.     

Spectral components that form UV absorption spectrum of Ce3+ and Ce(IV) valence states in matrix of photothermorefractive glasses

We have measured the UV absorption spectra of photothermorefractive glasses of the system Na₂O-ZnO-Al₂O₃-NaF-SiO₂ doped by cerium oxide in the range of (2.8–5.0) × 10⁴ cm⁻¹ (360–200 nm). The spectra have been processed by the method of dispersion analysis based on the analytical convolution model for the complex dielectric function of glasses. We show that the absorption band centered at 3.3 × 10⁴ cm⁻¹ (∼303 nm) that is attributed to the transition 2F _5/2 → 5d in the Ce³⁺ ion, is an envelope of three spectral components. The broad absorption range (3.5–4.7) × 10⁴ cm⁻¹ (200–270 nm) that is commonly interpreted as a charge transfer band of the Ce(IV) valence state, is an envelope of at least three spectral components.     

High-resolution photoacoustic and direct absorption spectroscopy of main greenhouse gases by use of a pulsed entangled cavity doubly resonant OPO

An entangled cavity doubly resonant optical parametric oscillator (ECOPO) has been developed to provide tunable narrow line width (<100 MHz) pulsed (8 ns) radiation over the 3.8–4.3 μm spectral range at a multi-kilohertz repetition rate with up to 100-W peak power. We demonstrate that coarse single mode tuning is obtained over the full spectral range of oscillation (300 cm⁻¹), while automated mode-hop-free fine tuning is carried out over more than 100 GHz. High-resolution spectra of main greenhouse gases (CO₂, N₂O, SO₂ and CH₄) have been obtained in good agreement with calculated spectra from the HITRAN database. These experiments outline the unique capabilities of the ECOPO for multi-gas sensing based on direct absorption as well as photoacoustic spectroscopy.     

Observation of ions with energies above 100 keV produced by the interaction of a 60-fs laser pulse with clusters

The x-ray spectra of a plasma generated by heating CO₂ and Ar clusters with high-intensity femtosecond laser pulses with q _las≃10¹⁸ W/cm² are investigated. Spatially resolved x-ray spectra of a cluster plasma are obtained for the first time. Photoionization absorption is observed to influence the spectral line profiles. The recorded features of the x-ray emission spectra definitely indicate the existence of a large relative number of excited ions (≃10⁻²–10⁻³) with energies of 0.1–1 MeV in such a plasma. Possible mechanisms underlying the acceleration of ions to high energies are discussed. It is shown that the experimental results can be attributed to the influence of ponderomotive forces in standing waves generated by the reflection of laser radiation from the clusters. Zh. éksp. Teor. Fiz. 115, 2051–2066 (June 1999)     

Synthetic spectrum of the stratosphere in the submillimeter region

A line-by-line and layer-by-layer optimized method is used for the fast computation of new high resolution spectra in the submillimeter region for the stratospheric medium. The results are shown as synthetic spectra between 10 and 40 cm⁻¹ and the presence of lines of minor gaseous constituents in the stratospheric medium is indexed. The purpose of the calculations is to determine better the spectral emission (better than 1 %) with a minimum computation time (less than 1’/cm⁻¹). The high resolution spectra (5.10⁻⁴ cm⁻¹) show excellent submillimeter emission lines; this opens a wide field of investigation for stratospherical studies.     

Measurements of high-pressure CO2 absorption near 2.0 μm and implications on tunable diode laser sensor design

A tunable diode laser (TDL) is used to measure the absorption spectra of the R46 through R54 transitions of the 20012←00001 band of CO₂ near 2.0 μm (5000 cm⁻¹) at room temperature and pressures to 10 atm (densities to 9.2 amagat). Spectra are recorded using direct absorption spectroscopy and wavelength modulation spectroscopy with second-harmonic detection (WMS-2f) in a mixture containing 11% CO₂ in air. The direct absorption spectra are influenced by non-Lorentzian effects including finite-duration collisions which perturb far-wing absorption, and an empirical χ-function correction to the Voigt line shape is shown to greatly reduce error in the spectral model. WMS-2f spectra are shown to be at least a factor of four less-influenced by non-Lorentzian effects in this region, making this approach more resistant to errors in the far-wing line shape model and allowing a comparison between the spectral parameters of HITRAN and a new database which includes pressure-induced shift coefficients. The implications of these measurements on practical, high-pressure CO₂ sensor design are discussed.     

NMR study of heterogeneity in pyridine-N-oxide...HCl crystal

An origin of narrow ¹H NMR signals in pyridine-N-oxide (PyO)...HCl crystal has been investigated by means of MAS, SPEDAS, NOESY and COSY techniques. Spectra of crystalline samples are compared with those of solid phase obtained from liquid PyO...HCl solutions (in acetonitile/H₂O) after the heterogeneous phase separation. It has been concluded that partially resolved peaks in ¹H NMR spectra of solids are related with heterogeneity of spin system and presence of different H-bond clusters of water molecules. NOESY spectra show no cross-peaks even at very long mixing time (500 ms). This indicates there is no exchange process between spins causing different peaks, and thus the corresponding molecular aggregates are captured in “islands of mobility8 without any channels sufficient for exchange. Appearance of MAS side bands as “pseudo8 cross-peaks in 2D NMR spectra using MAS/COSY technique is reported. In the case of accidental coincidence of spinning frequency (ω _MAS ) with spectral distances between some diagonal signals, intensive non-diagonal peaks are observed at the corresponding cross-positions. A misleading conclusion concerning spin coupling is easy to avoid using various ω _MAS . This work is dedicated to Professor Robert Blinc on the occasion of his 70^th birthday.     

The relaxation dynamics, iron valence state, and M?ssbauer effect in PFN ceramics

The dielectric properties, X-ray emission spectra, and M?ssbauer effect in ceramics made of PbFe_1/2Nb₁/₂O₃ (PFN) compound were studied. The relaxation dynamics revealed above Curie temperature TC at a frequency of 3 × 10⁻²–10⁵ Hz is described in detail. Analysis of the X-ray emission and M?ssbauer spectra showed that at room temperature (T = 300 K), the iron ions in PFN are mainly in the high-spin valence state Fe³⁺. The M?ssbauer spectral parameters obtained at T = (300, 353, and 393 K) indicate an octahedral environment for Fe³⁺ in both the ferroelectric and paraelectric phases.     

Optical functions of chalcopyrite CuGaxIn1-xSe2 alloys

We report pseudodielectric functions <ε> of the quaternary semiconductor alloys CuGa_xIn_1-xSe₂. Measurements were done in polycrystalline samples from 0.7 to 5.2 eV at room temperature by spectral ellipsometry. Accurate values of refractive indices n and extinction coefficients k representative of the bulk materials are obtained from the data. The structures observed in <ε> are analyzed by fitting the numerically differentiated spectra of d²<ε>(ω)/dω² to analytic line shapes. The obtained energies are related to given inter-band transitions by taking into account the electronic band structures of the ternary end-point compounds. Received: 20 December 2000 / Accepted: 30 May 2001 / Published online: 25 July 2001     

A local moment approach to the gapped Anderson model

We develop a non-perturbative local moment approach (LMA) for the gapped Anderson impurity model (GAIM), in which a locally correlated orbital is coupled to a host with a gapped density of states. Two distinct phases arise, separated by a level-crossing quantum phase transition: a screened singlet phase, adiabatically connected to the non-interacting limit and as such a generalized Fermi liquid (GFL); and an incompletely screened, doubly degenerate local moment (LM) phase. On opening a gap (δ) in the host, the transition occurs at a critical gap δ_c, the GFL [LM] phase occurring for δ<δ_c [ δ>δ_c] . In agreement with numerical renormalization group (NRG) calculations, the critical δ_c = 0 at the particle-hole symmetric point of the model, where the LM phase arises immediately on opening the gap. In the generic case by contrast δ_c > 0, and the resultant LMA phase boundary is in good quantitative agreement with NRG results. Local single-particle dynamics are considered in some detail. The major difference between the two phases resides in bound states within the gap: the GFL phase is found to be characterised by one bound state only, while the LM phase contains two such states straddling the chemical potential. Particular emphasis is naturally given to the strongly correlated, Kondo regime of the model. Here, single-particle dynamics for both phases are found to exhibit universal scaling as a function of scaled frequency ω/ω_m ⁰ for fixed gaps δ/ω_m ⁰, where ω_m ⁰ is the characteristic Kondo scale for the gapless (metallic) AIM; at particle-hole symmetry in particular, the scaling spectra are obtained in closed form. For frequencies |ω|/ω_m ⁰ ≫δ/ω_m ⁰, the scaling spectra are found generally to reduce to those of the gapless, metallic Anderson model; such that for small gaps δ/ω_m ⁰≪ 1 in particular, the Kondo resonance that is the spectral hallmark of the usual metallic Anderson model persists more or less in its entirety in the GAIM.     

Optical properties of new organic conductors based on the BEDT-TSeF molecule (the κ-(BETS)4Hg2.84Br8 superconductor and κ-(BETS)4Hg3Cl8 Metal) in the range 300–15 K

Polarized reflectance and optical conductivity spectra of single crystals of two new isostructural organic conductors based on the BEDT-TSeF molecule, namely, the κ-(BETS)₄Hg_2.84Br₈ superconductor (T _c =2 K) and the κ-(BETS)₄Hg₃Cl₈ metal, which undergoes a smooth transition to the dielectric state near 35 K, have been obtained in the spectral region 700–6500 cm⁻¹ at temperatures of 300–15 K. At 300 K, the spectra of both compounds are nearly identical and differ from the Drude spectrum characteristic of metals. The nature of the observed difference is discussed, and the spectra are described in terms of a cluster approach with inclusion of electron-electron correlations in the Hubbard approximation combined with the Drude model. The parameters of the theory were determined, including the electron transfer integrals between molecules in a cluster. The spectra in the conducting plane of the crystals were found to be essentially anisotropic, which should be assigned to specific features of in-plane interaction between molecules. The spectra of the superconductor and the metal become increasingly different as the temperature is lowered. The spectra of the metal obtained for T<150 K exhibit splitting of the broad electronic maximum in the mid-IR region into two bands, which is accompanied by a splitting of a vibronic feature deriving from electron interaction with intramolecular BETS vibrations of ν₃(A _g ) symmetry. No such splitting is observed in the superconductor spectra with decreasing temperature. __________ Translated from Fizika Tverdogo Tela, Vol. 46, No. 11, 2004, pp. 1921–1929. Original Russian Text Copyright ? 2004 by Vlasova, Drichko, Petrov, Semkin, Zhilyaeva, Lyubovskaya, Olejniczak, A. Kobayashi, H. Kobayashi.     

Effect of the fluorine substitution in ethyl groups of 1,4-distyrylbenzene on the fine structure fluorescence and fluorescence excitation spectra

The fine-structure fluorescence and fluorescence excitation spectra of conjugated chain compounds, 1,4-distyrylbenzene (DSB) and its fluorine-substituted derivative α,ω-1,4-distyrylbenzene, have been obtained by the Shpolskii method in an n-octane matrix at a temperature of 4.2 K. These spectra have been simulated by representing the band of each of the vibronic transitions as the sum of a zero-phonon line and a phonon wing with the corresponding parameters, such as the half-widths of the spectral lines and the Debye-Waller factors. Based on this simulation, the relative intensities of vibronic transitions have been determined and the frequencies of normal vibrations in the S ₀ and S ₁^* states have been refined. It has been found that the energy of the purely electronic transition in the molecule of the fluorine-substituted derivative is higher by 950 cm⁻¹ compared to the unsubstituted DSB. The parameters of the Franck-Condon and Herzberg-Teller interactions have been determined. The observed violation of the mirror symmetry between the conjugated spectra is explained by the interference of intramolecular interactions.     

Determination of temperature in a plasma jet emanating from a plasma torch with sectioned inter-electrode insert from the molecular emission spectrum of nitrogen

Results of application of a method for measuring the distribution of temperature in a nitrogen plasma jet emanating from a dc plasma torch with sectioned inter-electrode insert from the relative intensities of the molecular emission bands of nitrogen in the N₂ ⁺(B²Σ_u ⁺ − X²Σ_g ⁺) first negative and N₂(C³Π_u ⁺ − B³Π_g ⁺) second positive systems are reported. The emission spectra were registered using a small-size spectrometer with medium-range spectral resolution enabling a contour analysis of ro-vibrational bands in molecular emission spectra. The obtained distribution of temperature was compared with the distribution that was determined from the emission lines due to copper atoms and with the mean-mass plasma temperature of the air plasma jet.     

Raman spectra of various polymorphs of isotactic polypropylene

The Raman spectra of the α, γ, and smectic modifications of isotactic polypropylene (PP) are studied. The most significant spectral differences are observed in the frequency range around 2960 cm⁻¹ for the spectral doublet assigned to the asymmetric stretching vibrations of the CH₃ groups and in the frequency range around 800 cm⁻¹, which is used for analysis of the phase composition of isotactic PP. It is demonstrated that the peak positions and relative intensities of the doublet assigned to the asymmetric stretching vibrations of the CH₃ groups can be used to identify the polymorph modifications of isotactic PP.     

EPR of rare-earth ion clusters in mixed crystals Ba1−x La x F2+x doped with Yb3+ Ion

Electron paramagnetic resonance (EPR) spectra of Yb³⁺ ions in the mixed crystals (BaF₂)_1−x X(LaF₃) _x withx≈0.01 have been investigated by the electron spin echo method at a frequency of 94.9 GHz and compared with the spectra obtained by the continuous-wave EPR at a frequency of 9.5 GHz. Some spectral lines were identified within the framework of the simple cluster model proposed in our previous work (L. K. Aminov, R. Yu. Abdulsabirov, M. R. Gafurov, S. L. Korableva, I. N. Kurkin, S. P. Kurzin, R. M. Rakhmatullin, A. G. Ziganshin: Appl. Magn. Reson. 28, 41–53, 2005). Clusters consist of trigonal dipoles La−F and Yb−F (a rare-earth ion with a charge compensator) and are formed beginning with small concentrationsx≈0.001. The lines identified in the present work were attributed to the clusters with configurations Yb−F−La−F and La−F−Yb−F−La−F.     

Luminescence spectra fine structure for uranyl sulfate and oxalate crystals

Quasi-line low-temperature (T = 77 and 4.2 K) luminescence spectra of uranyl sulfates and oxalates have been recorded and analyzed. It has been shown that the spectral structure is determined by the manifestation of the internal and external vibrations of both the uranyl ion and molecular groups (SO₄)^2– and (C₂O₄)^2–bonded to the uranyl ion. The spectral line half-width is of the order of ≈5–7 cm^–1; the line shape, close to Lorentzian. The fluorescence spectra may be complicated by structural defects in the crystals.     

Fine structure of vibratory spectra and cation distribution in nonstoichiometric Mn-Zn ferrites

We have studied vibratory spectra in the range 200–700 cm⁻¹ of Mn−Zn ferrite crystal lattices containing both an iron excess or an iron deficit of up to 8 mole% relative to the stoichiometric compound. We performed a Kramers-Kronig analysis of the reflectance spectra, and a dispersion analysis of the spectra of the dielectric functions. The vibratory spectral band is quite complex. The compositional dependence of the individual component intensities is explained by a cation distribution model. According to this model the manganese cations in the octahedral sites are +3 valence in both iron-poor and iron-rich ferrites. Kazanskii State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 34–40, October, 1996.