Electron density redistribution in Sn-doped Bi2Te3

X-ray photoelectron spectroscopy is used to investigate the redistribution of the density of electronic states in the valence band, and of the binding energies and chemical shifts of core levels in bismuth telluride caused by introduction of impurity tin atoms. A substantial increase in the density of electronic states below the valence-band top at energies μ≈15–30 meV has been revealed. This feature in the energy spectrum accounts for the unusual behavior of the kinetic coefficients in p-Bi₂Te₃:Sn crystals. Fiz. Tverd. Tela (St. Petersburg) 41, 1969–1972 (November 1999)     

Structure of zinc-borate low-melting glasses derived from IR spectroscopy data

The IR spectra of glasses of the ZnO—SrO—B₂O₃ system with constant additions of PbO, Al₂O₃, and Li₂O (20 mol. % in sum) were studied. It is established that on replacement of B₂O₃ by ZnO, the structure of the glasses is characterized by the presence of groupings with the bridge bonds B^III— O—B^III, B^III—O—B^IV, B^IV—O—B^IV and end groups B^III— O⁻; ZnO practically exerts no influence on the coordination transition [BO₃] → [BO₄]. At a high content of ZnO, zinc ions are present in both a six-and a four-coordinated state. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 778–781, November–December, 2005.     

Site-specific valence-band X-ray photoelectron spectra of a SrTiO3 single-crystal by X-ray standing wave technique

Site-specific valence-band X-ray photoelectron spectra of SrTiO₃ (111) were successfully obtained by using X-ray standing wave technique. Contributions of the Ti and SrO₃ derived states to the valence-band spectra were clearly separated. The spectra provided not only site-specific but also bulk-sensitive information on the SrTiO₃ crystal because of the use of a high-energy synchrotron X-ray source (hν=4750 eV) for photoelectron excitation with the large escape depth. The electronic structures calculated by the DV-Xα method using a (Sr₈Ti₂₇O₁₀₈)⁹²⁻ cluster model well reproduced the observed structures in the valence-band spectra. The partial density of states of both Ti and Sr ions in SrTiO₃ were mainly distributed over the bottom of the valence-band to produce the covalent bonding with O ions.     

Superhyperfine structure of the EPR spectra of Ce<Superscript>3+</Superscript> ions in Li<Emphasis Type="Italic">R</Emphasis>F<Subscript>4</Subscript> (<Emphasis Type="Italic">R</Emphasis> = Y,Lu, Tm) double fluorides

The EPR spectra of Ce³⁺ impurity ions in LiYF₄, LiLuF₄, and LiTmF₄ double-fluoride single crystals have been investigated at a frequency of ∼9.3 GHz in the temperature range 5–25 K. The effective g factors of the ground Kramers doublet of the cerium ions in three crystals are close to each other (g _‖ = 2.737, g _⊥ = 1.475 for LiYF₄:Ce³⁺). A superhyperfine structure of the EPR spectrum of Ce³⁺ ions in the LiTmF₄ Van Vleck paramagnet has been observed in the external magnetic field B oriented along the crystallographic axis c (B ‖ c). The superhyperfine structure of the EPR soectra of the Ce³⁺ ions in the LiYF₄ and LiLuF₄ diamagnetic matrices is resolved for B ⊥ c. Possible factors responsible for this pronounced difference in the properties of the systems studied have been discussed.     

Investigation of the effect of uniaxial pressure on antiferromagnetic resonance in KFe11O17 Crystals

The deformation dependence of the resonance field in KFe₁₁O₁₇ single crystals was investigated by the AFMR method. The measurements were performed at T=77 K and ν=47.52 GHz for two orientations of the external pressure. The experimental data are discussed in terms of a model of a very simple easy-plane antiferromagnet taking account of the elastic and magnetoelastic contributions to the thermodynamic potential. The magnetostriction, magnetoelastic, and elastic contants are calculated and the results are λ=1.94×10⁻⁵, B ₁=2.75×10⁸ erg/cm³, and C ₁₁−C ₁₂=1.42×10¹³ erg/cm³, respectively. The alues of these constants imply that the origin of the initial gap in the AFMR spectrum is not of magnetoelastic origin. Fiz. Tverd. Tela (St. Petersburg) 40, 513–515 (March 1998)     

Use of cluster secondary ions for minimization of matrix effects in the SIMS depth profiling of La/B4C multilayer nanostructures

The elemental composition of La/B₄C multilayer metal structures is studied using SIMS on a TOF.SIMS-5 experimental setup. Analysis conditions that make it possible to considerably enhance the depth resolution are found. They include using low-energy O₂⁺ and Cs⁺ ions for sputtering and cluster secondary ions for registering matrix elements. The roughness evolution in the etching crater region is studied in a layer-by-layer analysis. It is shown that, at an incidence angle of 45° for sputtering ions, the rms roughness increases slightly (from an initial value of 0.5–0.7 nm) in the etching crater of the (La/B₄C)₇₀/Si structure at a depth of 0.5 μm. The profiles of elements in multilayer structures grown using two different types of magnetron systems with stationary and high-frequency discharges are compared. The main contaminations in the structures are determined.     

Interpretation of the soret band of porphyrins based on the polarization spectrum of N-methyltetraphenylporphin fluorescence

Low-temperature (77 K) absorption, fluorescence, and fluorescence-excitation spectra and the fluorescence polarization spectrum for N-methyl-meso-tetraphenylporphin (N-methyl-TPP) are measured. Based on the polarization spectrum the absorption spectrum in the visible region (a “generic” porphyrin spectrum) is interpreted. In particular, it is shown that the fifth absorption band (the “Longo band”) that manifests itself in some porphyrins is a Q_y(0–2) band and does not belong to the individual electron transition. Emphasis is placed on the region of the Soret band. It is inferred that at least two allowed electron transitions (G →B_x and G→B_y) polarized mutually perpendicularly manifect themselves in this region. The interpretation of the Soret band of porphyrins [2] that attributes this band to one electron transition G→B_x is thereby rejected. This interpretation is confirmed by computer modeling of the polarization spectrum. Special features of the experimental polarization spectrum are explained by a more developed vibrational structure and, possibly, a larger half-width of the B_x band than the half-width of the B_y band. The contribution of the states of intramolecular charge transfer to the formation of the Soret band is discussed. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 1, pp. 65–72, January–February, 1999.     

Investigation of the electronic structure of the SbSeBr cluster

The energy levels of valence bands (VB) in SbSeBr crystals were calculated for investigation of the photoelectron emission spectra of A⁵B⁶C⁷ — type crystals. The molecular model of this crystal was used for calculation of VB by the Density Functional Theory (DFT) and Unrestricted Hartree — Fock (UHF) methods. The molecular cluster consisting of 20 molecules of SbSeBr was used for calculations of averaged total density of states including atom vibrations. The spectra of averaged total density of states from VB in the SbSeBr cluster were compared with experimental photoelectron emission spectra from VB of A⁵B⁶C⁷ — type crystals. The results of comparison clarify that the atomic vibrations are one of possible reasons for the smoother appearance of the experimental X-ray photoelectron spectrum (XPS).      

First principles study of the electronic structures of erbium silicides with non-frozen 4f treatment

The electronic structures (especially 4f states) of hexagonal and tetragonal erbium silicides are investigated within density functional theory. Contrary to previous theoretical studies on these compounds, Er 4f electrons are treated as valence state electrons, explicitly taking into account the on-site Coulomb interactions. Total energy calculations show that the relaxed hexagonal ErSi_1.7 is more stable than the tetragonal structure, consistently with related experimental observations. The calculated total density of states of the hexagonal ErSi_1.7 agrees well with the experimental valence-band spectrum in a wide energy range from 0 to 12 eV below the Fermi level. In addition, our study indicates that the occupied 4f states in erbium silicides can also locate in the energy range of 0–4.0 eV below the Fermi energy, much different from the prediction of the previously adopted Er ion model.     

Singularity of the vortex density of states in d-wave superconductors

In d-wave superconductors, the electronic density of states (DOS) induced by a vortex exhibits a divergence at low energies: N _vortex(E) ∼1/|E|. This divergence is the result of gap nodes in the spectrum of excitation outside the vortex core. The heat capacity in two regimes, T ²/T _c ² ≫ B/B _c 2 and T ²/T _c ² ≪ B/B _c 2, is discussed. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 9, 641–645 (10 November 1996) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Recombination kinetics in nonlinear defective LiB3O5 crystals

A study of recombination kinetics in LiB₃O₅ (LBO) crystals by time-resolved luminescence and absorption spectroscopy is reported. An investigation of the kinetics of transient optical absorption (TOA) and luminescence under ns-scale electron-beam excitation performed within a broad temperature range of 77–500 K and a 1.2–5-eV spectral interval has established that the specific features in the recombination kinetics observed in LBO involve electronic, B²⁺, and hole, O⁻, trapping centers. The TOA and luminescence kinetics, as well as their temperature dependence, are interpreted by a model of competing hole centers. Relations connecting the kinetics parameters and the temperature dependence to the parameters of the main LBO point defects are presented. Fiz. Tverd. Tela (St. Petersburg) 40, 2008–2014 (November 1998)     

Free electronic states of UO2: Analysis of x-ray absorption by total multiple scattering

The experimentally observed x-ray absorption spectrum of oxygen in UO₂ is analyzed theoretically. The experimental absorption spectrum of oxygen is shown to agree well with details of the density of free p states of oxygen in the conduction band. It is found that a minimum cluster of atoms surrounding an absorbing oxygen ion required to reproduce all the details of the fine structure of the density of states at the bottom of the conduction band is of the order of 40 atoms. An analysis of the densities of the electronic states reveals the existence of hybridization of free p states of oxygen with s states of uranium in the conduction band of UO₂, as well as the exclusion of p states of oxygen by d states of uranium beyond the confines of the energy interval where they are localized. Fiz. Tverd. Tela (St. Petersburg) 41, 1385–1388 (August 1999)     

Quantitative conversion spectroscopy of the ultrasoft isomeric transition of uranium-235 and the electronic structure of uranium oxides

Combined measurements of conversion electron spectra and the decay constant (76.5 eV, (1/2)⁺→(7/2)⁻) of the E3-isomeric transition of the uranium-235 nucleus have been performed with collection of the isomer atoms on an indium surface. The conversion spectra are interpreted as corresponding to a mixture of two different oxides A and B of uranium, one of which (A) is similar to UO₂, and the other (B) consists of a uranium-oxygen cluster based on the linear uranyl group O-U-O. From a set of mixed experimental spectra conversion spectra have been found corresponding to the chemical states A and B of the isomer atoms, and the variation of the absolute intensities of the conversion lines has been quantitatively investigated for them by varying the chemical composition of the isomer atoms and the ratio between the intensities of various conversion lines of the B spectrum. Experimental ratios between the intensities of the conversion lines are compared with the expected ratios in accordance with the distribution of the 6p electron density in the uranyl group. It is concluded that the experimental data agree with the calculation and that abrupt violations of proportionality of the partial probabilities of conversion of the electron density near the nucleus are absent. In accordance with the hypothesis of proportionality of the partial probabilities of conversion, an experimental estimate is given of the degree of localization of the deep-lying uranium 6p _1/2 shell during formation of the chemical bond in the uranyl group: around 70% of the 6p _1/2 electron density remains in the quasi-atomic uranium shell and around 30% is transferred to hybrid molecular orbitals. Zh. éksp. Teor. Fiz. 112, 574–595 (August 1997)     

Electronic structure of phosphate glasses with a complex oxygen sublattice structure

Calculations of the electronic structure of phosphate glasses are performed in the MO LCAO x _α approximation discrete variation method. On the basis of an analysis of theoretical and experimental electronic spectra of the system BeO-P₂O₅ regularities are found in the formation of the valence band of alkaline-earth phosphate glasses with different types of anion sublattice. Data on the electronic structure are used to refine the models of short-range order; in particular, the possibility of oxygen in the threefold coordination state is confirmed. With the features of the spectrum of electronic states taken into account, localization of charge carriers, the nature of the optical transitions, and hole-transport phenomena are discussed. Fiz. Tverd. Tela (St. Petersburg) 39, 1366–1372 (August 1997)     

Phonons in red HgI2

A critical analysis of existing experimental and theoretical information on the lattice dynamics of the layered crystal α-HgI₂ is performed. It is shown that a satisfactory understanding of the character of the interatomic interaction and characteristic features of the phonon spectrum of this material can be obtained in a simple phenomenological model with eight parameters, assuming that E _g/B_1g degeneracy of the 29 cm⁻¹ Raman line is of a two-phonon nature. Fiz. Tverd. Tela (St. Petersburg) 40, 537–541 (March 1998)     

Rotational analysis of the 0–9, 0–10 and 0–11 bands of theA 2II u -X 2II g band system of (16O18O)+

High-resolution spectra of the 0–9, 0–10 and 0–11 bands of theA ²II _u —X ²II _g system of (¹⁶O¹⁸O)⁺ ion have been studied for their rotational structure. This study enables a direct determination of the Λ-doubling parameters of theA ²II _u andX ²II _g states. The model of ‘pure precession’ explains, though not entirely, the Λ-doubling of theX ²II _a state as arising out of its interaction with theB ² Σ _g ⁻ state. The Λ-doubling in theA ²II _u state was found insignificant.     

MINDO/3 calculation of the electronic structure of silicon nitride

The electronic structure of silicon nitride has been calculated by the semiempirical quantumchemical method MINDO/3 in the cluster approximation. The effect of cluster size and of boundary conditions on the partial density of one-electron states is analyzed. The results of the calculation are compared with experimental data on amorphous silicon nitride. The origin of a peak in the upper part of the valence band, which is seen in the SiL2,3 spectrum but not reproduced in the calculations is discussed. Fiz. Tverd. Tela (St. Petersburg) 39, 1342–1347 (August 1997)     

Superhyperfine structure of the EPR spectra of Nd<Superscript>3+</Superscript> and U<Superscript>3+</Superscript> ions in Li<Emphasis Type="Italic">R</Emphasis>F<Subscript>4</Subscript> (<Emphasis Type="Italic">R</Emphasis> = Y,Lu, Tm) double fluorides

The superhyperfine structure of the EPR spectra of impurity Nd³⁺ and U³⁺ ions in LiYF₄, LiLuF₄, and LiTmF₄ double-fluoride single crystals has been observed and discussed. In LiYF₄: Nd (g _| = 1.987, g _⊥ = 2.554) and LiTmF₄: Nd, the superhyperfine structure is observed at the orientation of the external magnetic field B in parallel to the c axis of the crystals and consists of nine components with a splitting of ∼15.4 MHz. In LiYF₄: U (g _| = 1.149, g _⊥ = 2.508) and LiLuF₄: U, the superhyperfine structure is observed at both B | c and B ⊥ c and consists of nine and eleven components, respectively, with a splitting of ∼21.5MHz. It should be noted that the resolution of the superhyperfine structure of the EPR spectrum of LiLuF₄: U³⁺ becomes significantly higher with a deviation from the orientation B ⊥ c.     

Electronic structure,ferroelectricity and optical properties of CaBi<Subscript>2</Subscript>Ta<Subscript>2</Subscript>O<Subscript>9</Subscript>

Using first-principles calculations based on density-functional theory in its local-density approximation, we investigated the Electronic structure, ferroelectricity and optical properties of CaBi₂Ta₂O₉ (CBT) for the first time. It is found that CBT compound has an indirect band gap of 3.114 eV and the O 2s and 2p states are strongly hybridized with the 6s states of Bi which belong to the (Bi₂O₂)²⁺ planes. The quite strong Ta–O and Bi–O hybridization is the primary source for ferroelectricity. Our results imply that the interaction between Bi and O is highly covalent. The anisotropy occurs mainly above 4 eV in the optical properties. The different optical properties have been discussed.     

NMR on 55Mn in the ferromagnetic Ni-substituted manganite La0.6Pb0.4Mn0.86Ni0.14O3

NMR on ⁵⁵Mn in the single-crystal manganite La_0.6Pb_0.4Mn_0.86Ni_0.14O₃ (T _C =242 K), which exhibits metallic conductivity below T _C , is investigated in the temperature range 61–215 K. At low temperatures, together with a line corresponding to the averaged hyperfine field at the ⁵⁵Mn nuclei (the averaging is due to the motion of electronic holes along Mn sites), the NMR spectrum also contains two lines corresponding to localized states Mn⁴⁺ and Mn³⁺. In the temperature range 100–200 K it is found that the complicated NMR spectrum is transformed into a single line on account of a delocalization of the holes in the e _g orbitals of manganese. A comparison of the NMR data with the temperature dependence of the resistivity suggsets that a wide distribution of charge-carrier mobilities exists in the crystal. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 8, 522–527 (25 October 1999)