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.     

Infrared spectra of brassinolide and castasterone steroid phytohormones and their 24-epi derivatives

Absorption bands in IR spectra of brassinolide, castasterone, and their 24-epi derivatives in the frequency range 3800–1000 cm^–1 have been interpreted. A number of spectral features distinguishing brassinolide from castasterone have been found. The conducted analysis shows that the structural differences manifest themselves in IR spectra of the investigated brassinosteroids in the region of stretching vibrations of CO–H, C=O, C–OH, C–O–C, CH₃, CH₂, and CH groups. The main distinctions in IR spectra of brassinolides and castasterones are due to the B ring structure.     

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)     

Raman scattering of light and IR absorption in carbon nanotubes

Raman light scattering and IR absorption spectra of samples containing multilayer carbon nanotubes in different stages of purification by the selective oxidation technique have been investigated. It was found that the Raman spectra of carbon nanotubes exhibit softening of the mode at 1582 cm⁻¹ corresponding to E _2g vibrations of graphite hexagons and a line at 120 cm⁻¹ due to the radial vibrations of nanotubes. In IR absorption spectra measured in the region of 0.07–0.3 eV, several sets of lines with a spacing of 15 meV (120 cm⁻¹) between lines of each group have been detected. We suggest that each group corresponds to electron transitions generating electron-hole pairs in semiconducting nanotubes and contains a phononless 00-line and its phonon replicas with spacing between them equal to the “breathing” mode energy of 120 cm⁻¹. Measurements of electric conductivity at a frequency of 9300 MHz indicate that, in addition to semiconducting nanotubes, the samples contain nanotubes with properties of a highly disordered semimetal. Zh. éksp. Teor. Fiz. 113, 1883–1891 (May 1998)     

Polarised raman and infrared spectra and vibrational analysis forα-naphthylamine

The Raman spectrum of polycrystalline α-naphthylamine was recorded in the region 100–4000 cm⁻¹. Polarisation measurements were made in CS₂ and CHCl₃ solutions. The infrared spectrum was recorded in nujol mull in the region 200–4000 cm⁻¹. The resolution was better than 2 cm⁻¹ and the accuracy of the measurements was within ± 2 cm⁻¹ for all the spectra. Vibrational assignments have been proposed for the observed frequencies. Out of the 54 normal modes of vibrations, 51 modes could be observed experimentally.     

Infrared spectra of S-and R-isomers of biologically active brassinosteroids

Comparative analysis of IR spectra of S-and R-isomers differing in the configuration of OH groups in the side chain of biologically active 24-epi-and 28-homocastasterones and 24-epi-and 28-homobrassinolides is carried out. Stretching vibration frequencies of H-bonded OH groups of isomers of corresponding brassinosteroids practically coincide. The optical density in maxima of these bands is higher in spectra of the R-isomers. Alteration in the configuration of the OH groups weakly influences also the band intensities of CH3, CH₂, and CH groups. Band intensities of stretching vibrations of associated C=O groups of S-and R-isomers also neglibibly differ from each other. Their frequency characteristics do not experience substantial changes. These features differ considerably in IR spectra of castasterones and brassinolides. For castasterones, the difference in frequencies of band maxima of free and bound C=O groups amounts to ∼15 cm⁻¹; for brassinolides, 23 cm⁻¹. Intensities of both bands are approximately equal in spectra of castasterones. The band intensity of free C=O groups of brassinolides is considerably lower than that of H-bonded ones. The above spectral differences can be used to identify these brassinosteroids. Frequencies of both symmetric and antisymmetric deformation vibrations of CH₃ and CH₂ groups are close in spectra of all brassinosteroids studied. The frequency of CH₂ in a CH₂-OC group belongs only to brassinolides; of deformation vibrations of CH in a CH-C=O group, to castasterones. The frequency of stretching vibrations of C-O-C and C-O groups is observed only in spectra of brassinolides. In the region 1130–900 cm⁻¹ of IR spectra of brassinosteroids, stretching vibrations of CC, CCH, and C-OH groups are predominantly observed. In the frequency range 1130–995 cm⁻¹, the optical density of band maxima of S-isomers is higher than that of R-isomers, which can be used to identify isomers. At the same time frequencies of corresponding bands of isomers practically coincide. Differences in the structure of the side chain of brassinosteroids do not influence essentially the frequency characteristics of the IR spectra. The exception is the band related to stretching vibrations ν(C23-OH) of the side chain which features a considerable frequency ν_max ≈ 983 cm⁻¹ only in spectra of R-isomers of homocastasterone and brassinolide. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 623–630, September–October, 2008.     

Vibrational studies of spinel LixMn2O4 (0.3≤x≤1.0) cathodes

We report on the vibrational properties of spinel LiMn₂O₄ and its electrochemically delithiated forms Li_xMn₂O₄. Raman scattering and infrared absorption spectra have been studied as a function of the delithiation content in the wavenumber range 50–700 cm⁻¹. Results show that lithium ions can be extracted at room temperature to obtain Li_x[Mn₂]O₄ (0.3≤x≤1.0) without disrupting the [Mn₂]O₄ array. The normal modes of the spinel LiMn₂O₄ have been discussed in the O _h ⁷ symmetry and vibrations due to lithium ions with their oxygen neighbors have been identified at ca. 400 cm⁻¹. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Vibrational studies of lithium-intercalated SnSySe2−y (0≤y≤2) layered compounds

We report the vibrational properties of lithium-intercalated SnS_ySe_2−y (0≤y≤2) layered compounds. Infrared absorption spectra have been recorded as a function of temperature in the frequency range 50–600 cm⁻¹. The new bands are interpreted as vibrational modes of lithium atoms against the nearest-neighbouring-chalcogen atoms located in the van der Waals gap. Results are analyzed in terms of stretching vibrations of Li-S₄ and Li-S₆ entities. From a comparison of the spectra, it is concluded that lithium ions are more likely to occupy tetrahedral sites in the lithium-rich phases. Using a simple model of lattice dynamics, the coupling force constants are determined and compared with those of the pristine materials. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

Analysis of electronic vibration spectra of tetrabenzoporphin molecules on the basis of calculations of their normal vibrations

Quasi-line fluorescence and fluorescence-excitation spectra of tetrabenzoporphin (H₂TBP) and its deuterated derivative (D₂TBP) in n-octane at 77 K were measured and analyzed. A calculation of normal vibrations of the H₂TBP and D₂TBP molecules has been performed. The normal vibrations of these molecules were calculated with the use of the valence force fields of porphin and phenanthrene (the direct spectral problem was solved). Good agreement between the calculated and measured frequencies of the investigated normal vibrations has been obtained without correction of the transfered force constants. A detailed interpretation of the fluorescence spectra obtained is presented. It is shown that on deuteration of H₂TBP, the behavior of the quasi-lines in the fluorescence-excitation spectra in the region of resonance with the S₂←S₀ transition becomes more complex. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 3, pp. 375–382, May–June, 1999.     

Infrared absorption spectra and structure of TiO2-SiO2 composites

The composites xTiO₂-(1−x)SiO₂ (x = 0.1, 0.5, 0.9) were obtained by coprecipitation from solutions of alkoxides: tetraethoxysilane (TEOS) and titanium tetraisopropoxide (TIPT). Intermolecular interaction of the components of the composite is apparent in the IR absorption spectra in the 928–952 cm⁻¹ region, and is connected with bending vibrations of the Si-O-Ti bond. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 724–728, September–October, 2008.     

Long-lived excited states and photoluminescence excitation spectra in single crystals of fullerene C60

Photoluminescence, optical absorption spectra, and photoluminescence excitation spectra were measured on large (2–3 mm), very pure crystals of fullerene C₆₀ at 5 K. It is shown that the main contribution to the photoluminescence of these crystals is from singlet and triplet excitons captured on crystal defects. The concentration of these defects does not exceed 10¹⁸ cm⁻²³, and the lifetime of triplet excitons on these defects is about 3 ms. It is shown that the symmetry distortion of the C₆₀ molecules at the defects is rather large and causes the oscillator strength of the zero-phonon optical transitions to be comparable to the most intense optical transitions with the participation of intramolecular vibrations. Zh. éksp. Teor. Fiz. 113, 734–746 (February 1998)     

Spectral characteristics of heterocyclic compounds with a chain structure, cooled in an ultrasonic jet

We have recorded the fluorescence excitation spectra of three heterocyclic compounds with a chain structure [BPO (2-phenyl-5-(4-diphenylyl)oxazole), POPOP (1,4-di[2-(5-phenyloxazolyl)]benzene, and TOPOT (1,4-di[2-(5-n-tolyloxazolyl)]benzene] and the fluorescence spectra of POPOP, under conditions where the molecules were cooled in an ultrasonic helium jet. A line structure is observed in the spectra of POPOP and TOPOT; for the BPO molecules, whose configuration changes considerably during electronic excitation, vibrational structure is apparent only in the low-frequency region of the excitation spectrum, and a diffuse spectrum is recorded starting from ν ₀ ⁰ + 200 cm⁻¹. For all the compounds, in the spectra we recorded vibrations with frequencies up to 100 cm⁻¹, arising due to the flexibility of the molecular structure. The rotational contours of the lines for the electronic and vibronic transitions of the POPOP molecules (T_rot = 10.5 K) and TOPOT molecules (T_rot = 15 K) are structureless and bell-shaped. The degree of polarization of the fluorescence P_fl for the jet-cooled POPOP molecules for excitation of vibrations along the absorption band up to 2000 cm⁻¹ above ν ₀ ⁰ is practically constant (∼8.4%) and matches P_fl for high-temperature vapors. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 728–734, November–December, 2006.     

Luminescence of oxygen molecular ion in neodymium-doped yttria

Pulsed cathodoluminescence spectra of Nd³⁺:Y₂O₃ compacts registered after their annealing in air at a temperature above 950°C exhibit a structured band in the range 610–660 nm with four well-resolved components located at wavelengths of 620.6, 630.6, 645.3, and 655.6 nm. At the same time, the lattice parameter of the cubic yttria increases, and the color of samples changes from light blue to yellowish. In addition, the nearly complete absorption of the intrinsic luminescence band of yttria is observed in the range of 380–600 nm with a center at λ = 485 nm. We assume that these effects are caused by oxygen molecular ions O₂⁻, which are formed in cubic yttria due to the penetration of oxygen into natural anion vacancies. The frequencies of vibrations of the ground and excited states of the oxygen molecular ion has been determined.     

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.     

Fluorescence studies of CS2 and SO2 at 121.6, 73.6–74.4 and 58.4 nm

The fluorescence spectra of CS₂ and SO₂ have been studied at three incident photon wavelengths of 121.6, 73.6–74.4 and 58.4 nm and relative production cross sections for different product states have been measured. The CS(A ¹Π→X ¹Σ⁺) system between 240 and 290nm has been obtained when CS₂ is photoexcited at 121.6nm whereas CS ₂ ⁺ (B ²Σ _u ⁺ →X ²Π _g ) and CS ₂ ⁺ (A ²Π _u →X ²Π _g ) systems have been produced between 276 and 295 and 437 and 555nm respectively when excited by both the incident photon wavelengths of 73.6–74.4 and 58.4nm. The fluorescence spectra of SO₂ obtained at 121.6 and 73.6–74.4nm include the vibrational bands of SO(A ³Π→X ³Σ⁻) and SO(B ²Π⁻→X ³Σ⁻) systems from 240 to 268 and 268 to 442nm respectively whereas the emission spectrum at 58.4nm, has contributions from the two SO systems and SO⁺(A ²Π→X ²Π) system. In all these emission spectra, the fluorescence bands of different systems have been analyzed and their relative production cross sections have been measured. The results obtained in the present investigations have been compared with a few recent reliable measurements reported in literature.     

Dynamics of formation of the composition,structure, and spectral characteristics of uranium complexes

We have examined general rules for the change of frequency of stretching vibrations of UO ₂ ²⁺ (uranyl) as a function of U-O and uranium-ligand interatomic distances. We analyzed the behavior of these frequencies as a function of donor number (DN) of the organic ligand by studying IR absorption and visible luminescence spectra. A linear correlation was found. We proposed spectroscopic methods for determining the DN of ligands, which are difficult to estimate by other methods, and the composition and structure of uranium complexes. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 4, pp. 433–438, July–August, 2007.     

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)     

Spectroscopic properties of Pr<Superscript>3 + </Superscript>-doped erbium oxalate crystals

Spectroscopic properties of praseodymium ions-doped erbium oxalate (Er₂(C₂O₄)₃ · nH₂O) crystals have been investigated. The crystals were grown by hydro silica gel method under suitable pH conditions and by single diffusion method. The well-grown crystals are bright and transparent. The dark green colour of these crystals changes with the variation of the concentrations of the dopant ions. The absorption spectra have been measured in the region 200–800 nm at room temperature. Judd–Ofelt intensity parameters for f–f transitions of the Pr³⁺ ions have been determined as Ω₂ = 166.7, Ω₄ = 1.103 and Ω₆ = 2.898. Analyses of the absorption spectra also show a possible energy transfer from the host material to the dopant.     

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.