Infrared spectra of catalysts and adsorbed molecules

The infrared absorption spectra of water adsorbed on Al₂O₃ and NiO-Al₂O₃ catalysts have been studied in the range 4000–1200 cm^–1. For all the catalysts, broad bands are observed at 3400 and 1640 cm^–1, characteristic of the stretching and bending vibrations of the OH groups in liquid water. The bands observed in the spectrum of alumina prepared from suspension in isopropyl alcohol are produced by water molecules and isopropyl alcohol molecules absorbed on the catalyst surface. The influence of treatment with heavy water and thermal treatment on the position of the infrared absorption bands in the spectrum of alumina is discussed.     

Evolution of the Electroluminescence Spectra and the Acoustic Emission of the Epitaxial Structures of GaAsP

The dependence of the spectral position of the electroluminescence bands of epitaxial light-emitting diode n ⁺–n–p structures (GaAs_0.15P_0.85) on the density of a direct heterojunction current at different successive instants of time — before an acoustic emission and after it — has been revealed. The shifts of the electroluminescence bands accompanied by acoustic emission can be divided into three types according to the density of the current: (1) short-term shifts due to relaxation of the defect structure of a sample — at relatively low currents, (2) the magnitude of the reverse shift being determined by the current density — at large currents, and (3) formation of an IR band (1.5–1.1 eV) with irreversible degradation changing in the red (1.75 eV) and green (2.19 eV) bands of the electroluminescence spectrum — at ultrahigh currents (100–200 A/cm²).     

Influence of Oxygen Vacancies on the Luminescence Spectra of Y2O3 Thin Films

Luminescence spectra of Y₂O₃ thin films annealed in air and in vacuum are investigated. It is established that the presence of oxygen vacancies leads to a decrease in the intensity of the luminescence band with a maximum at 3.4 eV (related to emission of selflocalized Frenkel excitons describing the excited state of a molecular ion (YO₆)^9–) and of the luminescence band with a maximum at 2.9 eV (related to the anion sublattice). It is revealed that the oxygen vacancies also lead to a decrease in the luminescence intensity in the 2.60, 2.35, 2.10. 1.90, and 1.70 eV bands that are related to radiative recombination in the donor–acceptor Y³⁺–O^2– pairs. The donor–acceptor distances are calculated.     

Optical absorption in films of V2O5 and vanadium-phosphorus glasses

The results of an investigation of the spectral dependence of the absorption coefficient of amorphous and polycrystalline films of V₂O₅ and films of vanadium-phosphorus glasses in the 0.3–5 eV energy range are presented in this paper. It is shown that the fundamental absorption edge is determined by direct forbidden transitions; the nature of the absorption bands detected below the fundamental absorption edge is discussed.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No.2, pp. 102–106, February, 1976.     

Electron energy loss spectra from polycrystalline Cr and Cr2O3 before and after surface reduction by Ar bombardment

Electron energy loss spectra (ELS) have been obtained from polycrystalline Cr and Cr₂O₃ before and after surface reduction by 2 keV Ar⁺ bombardment. The primary electron energy used in the ELS measurements was systematically varied from 100 to 1150 eV in order to distinguish surface versus bulk loss processes. Two predominant loss features in the ELS spectra obtained from Cr metal at 9.0 and 23.0 eV are assigned to the surface and bulk plasmon excitations, respectively, and a number of other features arising from single electron transitions from both the bulk and surface Cr 3d bands to higher-lying states in the conduction band are also present. The ELS spectra obtained from Cr₂O₃ exhibit features that originate from both interband transitions and charge-transfer transitions between the Cr and O ions as well as the bulk plasmon at 24.4 eV. The ELS feature at 4.0 eV arises from a charge-transfer transition between the oxygen and chromium ions in the two surface layers beneath the chemisorbed oxygen layer, and the ELS feature at 9.8 eV arises from a similar transition involving the chemisorbed oxygen atoms. The intensity of the ELS peak at 9.8 eV decreases after Ar⁺ sputtering due to the removal of chemisorbed oxygen atoms. Sputtering also increases the number of Cr²⁺ states on the surface, which in turn increases the intensity of the 4.0 eV feature. Furthermore, the ELS spectra obtained from the sputtered Cr₂O₃ surface exhibit features characteristic of both Cr⁰ and Cr₂O₃, indicating that Ar⁺ sputtering reduces Cr₂O₃. The fact that neither the surface- nor the bulk-plasmon features of Cr⁰ can be observed in the ELS spectra obtained from sputtered Cr₂O₃ while the loss features due to Cr⁰ interband transitions are clearly present indicates that Cr⁰ atoms form small clusters lacking a bulk metallic nature during Ar⁺ bombardment of Cr₂O₃.     

Studies on the origins of the absorption spectra in PbWO4 crystal

The electronic structures and absorption spectra for both the perfect PbWO₄ (PWO) crystal and the three types of PWO crystals, containing V_Pb²⁻, V_O²⁺ and a pair of V_Pb²⁻-V_O²⁺, respectively, have been calculated using CASTEP codes with the lattice structure optimized. The calculated absorption spectra indicate that the perfect PWO crystal does not occur absorption band in the visible and near-ultraviolet region. The absorption spectra of the PWO crystal containing V_Pb²⁻ exhibit seven peaks located at 1.72 eV (720 nm), 2.16 eV (570 nm), 2.81 eV (440 nm), 3.01 eV (410 nm), 3.36 eV (365 nm), 3.70 eV (335 nm) and 4.0 eV (310 nm), respectively. The absorption spectra of the PWO crystal containing V_O²⁺ occur two peaks located at 370 nm and 420 nm. The PWO crystal containing a pair of V_Pb²⁻-V_O²⁺ does not occur absorption band in the visible and near-ultraviolet region. This leads to the conclusions that the 370 and 420 nm absorption bands are related to the existence of both V_Pb²⁻ and V_O²⁺ in the PWO crystal and the other absorption bands are related to the existence of the V_Pb²⁻ in the PWO crystal. The existence of the pair of V_Pb²⁻-V_O²⁺ has no visible effects on the optical properties. The calculated polarized optical properties are well consistent with the experimental results.     

Photo- and thermostimulated processes in α-Al2O3

We reported on the recombination processes determined by the release of electrons from defects connected with the dosimetric 430 K thermostimulated luminescence (TSL) peak as well as with the 260 K TSL peak. These TSL peaks appear in thermochemically reduced α-Al₂O₃ crystals containing hydrogen and emission of these TSL peaks corresponds to luminescence of the F-center. The X-ray exposure or UV excitation in the absorption band of F-centers at 6.0 eV of reduced α-Al₂O₃ crystals doped with acceptor impurities results in the appearance of a broad anisotropic complex absorption band in the spectral region 2.5–3.5 eV and in the appearance of a predominant TSL peak at 430 K. Above 430 K the above-mentioned broad absorption band disappears. Optical bleaching of the 2.5–3.5 eV band is accompanied by the disappearance of the 430 K TSL peak and results in F-center emission. The X-ray or UV excitation of reduced α-Al₂O₃ crystals with donor-type impurities results in the appearance of an anisotropic absorption band at 4.2 eV and the appearance of a dominant TSL peak at 260 K. Above 260 K the 4.2 eV absorption disappears and photostimulated luminescence (PSL) of the F-center recombination luminescence in the 4.2 eV region is no longer observed. Optical bleaching of the 4.2 eV absorption band is accompanied by the disappearance of the 260 K TSL peak. The successful use of reduced α-Al₂O₃ in dosimetry needs the optimization of the concentration of all components (acceptors, hydrogen, intrinsic defects) involved in the thermo- and photostimulated processes.     

Optical studies on free-standing polypyrrole films by the photopyroelectric method

Optical spectra of free-standing polypyrrole films were investigated by a novel PhotoPyroElectric (PPE) method. The reflection and absorption spectra in the range 2000–25000 cm^–1 of TsO^–- and ClO ₄ ^su– -doped polypyrrole films were obtained with an experimental setup comprising two pyroelectric sensors. The absorption bands due to electronic transitions to the bonding and antibonding bipolaronic levels appear at 11 000 and 21 500 cm^–1, respectively. Some relevant details in the polypyrrole spectrum in the 2000–5000 cm^–1 range were observed. The absorption band located at 3400 cm^–1 is characteristic for NH stretching vibration. The bands in the 2300–2500 cm^–1 range are ascribed to the vibration of N⁺H groups containing positively charged nitrogen. The PPE spectra also reveal changes of the electronic and vibrational absorption bands after polymer reduction and HCl treatment.     

O−−-Lücken-Dipole in Alkalihalogenidkristallen

Dielectric loss measurements are reported for KBr, KCl, and NaCl crystals containing O^?? ions. The frequency and temperature dependences can be well represented by a Debye curve. The dipole moment found immediately after quenching is interpreted as being due to O^?? ions associated with anion vacancies. Activation energies for reorientation of the ion are E₀=0.59 eV for KCl, 0.54 eV for KBr and 0.61 eV for NaCl. Fluorescence bands were found in freshly quenched KCl crystals at 470 nm and 1.05 μm and are attributed to isolated dipoles. Dielectric losses decreased and the optical absorption changed during annealing due to the collection of centers into aggregates. A detailed analysis of the kinetics for KCl indicates the formation of double dipoles as the first step. The energy of association is E_A=0.85 eV. Earlier measurements of absorption, fluorescence and photochemical coloring are reinterpreted on the basis of the proposed model in which an O^?? center is thought of as a O^?? ion associated with an anion vacancy.     

Optical properties of iron alloys with heavy rare-earth elements

Spectral-ellipsometric measurements by the Beatty method were made in the region from 1 eV to 4 eV at temperatures of 100, 293, and 700 K to determine the relation between the distinctive features of the optical absorption spectrum and the principal parameters of the electron energy spectrum in iron alloys with rare-earth elements. The fundamental bands of interband optical absorption of Fe₂-R alloys (R=Gd, Ho, Er) in the region 2.8–3.1 eV are formed by indirect transitions from d-like states, which are genetically bound to 3d–5d electrons of the transition metal and the rare-earth metal, in a state above the Fermi level.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 12, pp. 64–67, December, 1988.We thank our senior research colleague V. A. Domyshev for supplying the samples and carrying out the x-ray structure analysis.     

Ab initio calculations of electronic structures of SrMoO4 crystals containing F and F color centers

The electronic structures of SrMoO₄ crystals containing F and F⁺ color centers with the lattice structure optimized are studied within the framework of the fully relativistic self-consistent Dirac–Slater theory, using a numerically discrete variational (DV-Xα) method. From the calculation, it is concluded that F and F⁺ color centers have donor energy level in the forbidden band. The electronic transition energies from the donor level to the bottom of the conduction band are 1.855 eV and 2.161 eV, respectively, which correspond to the 670 nm and 575 nm absorption bands. It is predicted that the 670 nm and 575 nm absorption bands originate from the F and F⁺ centers in SrMoO₄ crystals.     

Photoluminescence of aqueous solutions of uranyl nitrate containing sodium tetrametaphosphate

Solutions (10^–5 to 5×10^–2 M) of UO₂(NO₃)₂ have been used in the presence of 2 wt.% Na₄P₄O₁₂, with excitation by a mercury arc over the range 3200–3800 Å. The emission and absorption spectra of the complex are reported; the first is narrow and has peaks at 4910, 5150, and 5400 Å. This spectrum is the same whether the tetrametaphosphate anion has the chair configuration or the boat one.     

Luminescence of Donor‐Acceptor Pairs in Compounds of Yttrium and Scandium Oxides

The luminescence spectra of Sc₂O₃, Y₂O₃, and Y₂GeO₅ ceramics and thin films exposed to laser and cathode excitation were investigated. The investigation of the properties of longwave luminescence bands in Sc₂O₃ with maxima at 2.65, 2.35, and 2.05 eV, in Y₂O₃ with maxima at 2.60, 2.35, and 2.10 eV, and also in Y₂GeO₅ with maxima at 2.55, 2.25, and 2.00 eV point to the fact that they are caused by radiative recombination of the excited donoracceptor pairs Sc³⁺ (or Y³⁺)O^2–.     

Luminescence of Thin Bi2W2O9 Films

The luminescence spectra of thin Bi₂W₂O₉ films have been investigated. The spectra were separated into elementary components by the Alentsev–Fock method. The radiation band with a maximum at 2.43 eV in the luminescence spectrum of Bi₂W₂O₉ has been assigned to the Frenkel autolocalized excitons. The luminescence bands with maxima at 2.10 and 1.90 eV have been assigned to the emission of the centers whose energy levels are located in the forbidden band. The luminescence of the Bi₂W₂O₉ films is due to the emission of the WO₆ complex.     

The absorption of pulsed CO2-laser radiation by tetrafluorosilane at various wavenumbers,fluences, pulse durations,temperatures, optical path lengths and pressures of absorbing and non-absorbing gases

The absorption of three linesP(30) (1037.4 cm^–1),P(36) (1031.5 cm^–1) andP(40) (1027.4cm^–1) of the pulsed CO₂ laser (00⁰1–02⁰0 transition) by SiF₄ was examined at various pulse energies, pulse durations, temperatures, optical path lengths and pressures of this compound and several non-absorbing gases. In addition, the low-intensity infrared absorption spectrum of tetrafluorosilane was compared with high-intensity absorption data for all lines of the laser. The experimental dependences demonstrate nonlinear features of the absorption phenomena originating from the high power of the incident radiation and collisions of absorbing molecules with surroundings. These effects are included in the analytical formula, being an extended form of the Lambert-Beer law. which reasonably approximates all experimental data. The importance of the results obtained for understanding general features of multiphoton absorption and for revealing potential applications of SiF₄ as a sensitizer for the infrared region is presented in brief.     

Configuration interaction calculations for the ground and excited states of ozone and its positive ion: Energy locations and transition probabilities

Large-scale configuration interaction calculations (including energy extrapolation) are reported for the various states of ozone and its positive ion. The first four dipole-forbidden electronic transitions in the O₃ spectrum are calculated to occur at 1.20, 1.44, 1.59, and 1.72 eV, respectively, while the corresponding low-energy-allowed species known as the Chappuis, Huggins, and Hartley bands are predicted to possess vertical excitation energies of 1.95, 3.60, and 4.97 eV, respectively. These results all appear to fit in quite well with the observed location of the pertinent spectral features, with respect to both energy and intensity. The 5- to 8-eV region of the ozone spectrum is found to be characterized by a series of double-excitation transitions out of the highest three occupied orbitals to the lowest unoccupied 2b₁(π^*) species. The strong features observed at 9.3 and 10.2 eV are thereupon calculated to result primarily from transitions into the 7a₁ (σ^*) MO (calculated 9.29 and 10.05 eV) and in the former case also from the 3s members of the various O₃ Rydberg series (calculated 9.21 and 9.38 eV). Finally the order of the first three ip's is found to be 6a₁, 4b₂, and 1a₂, while the feature in the neighborhood of 16 eV is attributed to a shake-up state of ²B₁ symmetry.     

Electrophysical and photoelectric properties of (CdSe)1−x(CuInSe2)x solid solutions

The results are given of measurements of the electrophysical properties in the interval of temperatures 300–900°K and of the photoelectric properties at 300°K of (CdSe)_1–x–(CuInSe₂)_x solid solutions. It is shown that the electrophysical and photoelectric properties of the solid solutions depend on the composition and temperature. The forbidden-band widths calculated from the temperature dependence of the conductivity and from the photoconductivity spectrum, respectively, vary from 1.68 and 1.77 eV for initial compound CdSe to 1.25 and 1.18 eV for the solid solution Cu_0.1Cd_0.9In_0.1Se_1.1.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 41–43, January, 1992.     

Oscillator strength of F2 − colour centres in LiF crystal

The absorption cross-section integral and the oscillator strength of the 960 nm absorption band due to F₂ ^– colour centres in LiF crystal is determined at room temperature from the absorption cross-section spectrum of the F₂ ^– centres obtained from saturable absorption studies. A comparison with previous results is made.     

Absorption Spectra of Single Crystals of EuGa2S4 and EuGa2S4:Co

The optical properties of EuGa₂S₄ and EuGa₂S₄:Co single crystals in a range of temperatures from 77 to 300 K are investigated. The single crystals are obtained by the Bridgman method and are characterized by tetragonal syngony. The behavior of the optical transitions in the photon energy range 1.70–2.45 eV and the temperature range 77–300 K is determined. It is established that in the energy range 1.77–1.90 eV absorption is associated with transitions of the Co²⁺ ion, while in the range 2.20–2.40 eV, with indirect allowed optical transitions.     

Eu<Superscript>3+</Superscript> doped yttrium oxysulfide quantum structures—structural,optical and electronic properties

Small particles of trivalent europium doped yttrium oxysulfide nanocrystals (ϕ ∼ 7 nm) were synthesized using sol–gel polymer thermolysis. The nanocrystals show significant change in the excitation bands corresponding to fundamental absorption and charge transfer absorption bands. The optical spectra essentially comprise of two parts: fundamental absorption (∼260 nm) and Eu³⁺–X²⁻ ligand (O²⁻/S²⁻) charge transfer (∼290 nm) bands. They show significant blue shifts (0.24–0.30 eV), respectively, with respect to the bulk counterpart. These may be explained by considering possible size dependent changes associated with quantum confinement effect in this large bandgap semiconductor system. FT-IR spectra revealed the difference in chemisorbed species between bulk and nanocrystalline samples. The results of the solid-state photo-induced electrical impedance spectroscopy studies are reported.