Type I FA (Rb, Cs) and II FA (Li, Na) tunable laser activities and donor-acceptor properties of O and O at KCl (001) surface: first principle calculations

Type I F_A (Rb⁺, Cs⁺) and II F_A (Li⁺, Na⁺) tunable laser activities, adsorptivity and donor-acceptor properties of O and O⁻ adsorbates at the flat surface of KCl crystal were investigated using an embedded cluster model and ab initio methods of molecular electronic structure calculations. Ion clusters were embedded in a simulated Coulomb field that closely approximates the Madelung field of the host surface, and the nearest neighbor ions to the defect site were allowed to relax to equilibrium. Based on the calculated Stokes shifted optical transition bands, F_A tunable laser activities were found to be inversely proportional to the size of the dopant cation (Li⁺, Na⁺, Rb⁺, Cs⁺) relative to the host cation (K⁺). This relation was explained in terms of the axial perturbation of the impurity cation. The probability of orientational bleaching attributed to the RES saddle point ion configuration along the 〈110〉 axis was found to be inversely proportional to the size of the dopant cation, with activation energy barriers of ca. 0.44-3.34 eV. Surface relaxation energies of type II F_A centers were more important than those of type I F_A centers. In terms of defect formation energies, the products of type II F_A center imperfection were more stable than those of type I F_A. The difference between F or F_A band energies and exciton bands depended almost exclusively on the size of the positive ion species. As far as the adsorptivity of O and O⁻ is concerned, the results confirm that surface imperfection enhances the adsorption energies by ca. 4.38-16.37 eV. O and O⁻ penetrate through the defect-containing surface. The energy gap between the adsorbate and the defect containing surface and the donor-acceptor property of adsorbate play the dominant role in the course of adsorbate substrate interactions and the results were explained in terms of electrostatic potential curves and Mulliken population analysis.     

Composite structure of the V1 band in strongly sodium-doped KBr

A detailed analysis was made of the thermal annealing of V₁ band in strongly Na-doped KBr crystal. It was found that two components (406 and 415 nm) exist in V₁ band region in such crystals. The 415 nm component, which increases with a decrease of the 406 nm component and shows a 〈110〉 type dichroism, has been assigned to be H_AA and/or H_A'A band.     

The elastic interaction of the H center with A Rb+ ion in KBr crystals

The formation and the thermal annealing of H and F centers in KBr:Rb are studied and discussed in terms of the elastic interaction between H centers and Rb⁺. The difference in the interaction during dynamical and thermal motions of H centers is emphasized.     

Temperature dependence of the dynamic interstitial interactions in potassium bromide

Formation of the H and H_A centers in Na⁺-doped KBr within the time constant of the thermal annihilation of the H center is measured between 80 and 200K and it is shown that the volume of the interaction of the radiation-induced replacement sequence of an interstitial halogen with a Na⁺ impurity increases with an activation energy of (0.025 ± 0.005) eV as the temperature rises.     

H-center interactions during thermal annealing in KBr

Formation of the V₄-center and the H_A-center during thermal annealing in pure and Na⁺- and Li⁺-doped KBr, X-irradiated at low temperatures, is studied. It is found that these centers are produced accompanied with the annealing of the H-center at the second stage, of which the reaction order is two. The dependence of the concentration of Na⁺ impurity on the formation yield of the V₄-center by thermal annealing is studied and it is shown that the yield of the V₄-center formation is proportional to the square of the concentration of the H-center annealed at the second stage. This result confirms the former di-H-center model of the V₄-center.     

Absorption- and uniaxial stress experiments in the a band of Pb2+ centres in KBr,RbBr, KI and RbI

The absorption lineshape and the stress induced dichroism of the A band of Pb²⁺ centres in KBr, RbBr, KI and RbI have been measured as a function of temperature from 4 K to room temperature. The moments of the absorption bands and of the dichroic spectra have been determined, and the effective coupling constants of the linear electron-lattice interactions of the ¦A〉 state as well as the frequencies of the interaction modes have been evaluated. Above 200 K the temperature dependence of the moments gives strong evidence that nonlinear electron-lattice interactions are important, particularly in the case of KBr:Pb²⁺.     

On the origin of the visible emission in KBr:Tl and KCl:Tl crystals

The intensity of the visible emission of KBr:Tl at 440 nm is shown to increase linearly with the absorption in the A₁ band at 4.64 eV (267 nm). The latter band increased with the square of the Tl⁺ ions concentration, which supports its assignment to thallium dimers. Similarities in behavior between the 440 nm emission of KBr:Tl and the 475 nm emission of KCl:Tl suggest that the latter is also related to dimers. This is supported by the superlinear dependence of this emission on the Tl⁺ ion concentration. Deviations ofthe superlinearity from the square dependence expected for dimers is explained by the overlap between the weak dimer absorption and the very strong A-band.The 440 nm emission of KBr:Tl was found to be excited only in the A₁ component of the dimer absorption and not in the stronger A₂ component. This indicates that the emission process may be compound.     

Luminescence of Tl<Superscript>+</Superscript> ions in a KZnF<Subscript>3</Subscript> crystal

The luminescence spectra of a KZnF₃: Tl⁺ crystal are investigated in the energy range from 4.75 to 5.9 eV at temperatures of 10–300 K upon excitation into the A absorption band (5.7–6.3 eV). At T=300 K, the luminescence spectra exhibit an intense band with a maximum at 5.45 eV, which is attributed to single Tl⁺ ions substituted for K⁺ ions. The 5.723-eV intense narrow band observed at T<20 K is assigned to the ³Γ_1u-¹Γ_1g zero-phonon transition, which is weakly allowed by the hyperfine interaction. The luminescence decay is studied as a function of temperature. The main characteristics of the luminescence spectra are adequately described in terms of the semiclassical theory based on the Franck-Condon principle and the Jahn-Teller effect for an excited sp configuration of the Tl⁺ ion with the use of the parameters obtained earlier from analyzing the absorption spectra of the system under investigation.     

Untersuchung von Neutronenreaktionen mit Emission von α-Teilchen an Na23 im Energiebereich von 12,6 bis 18,7 MeV

TheA band of Tl⁺ centers in mixed crystals of KCl—KBr, KBr—KI, and KCl—KI is split into several subbands at low temperatures. The degree of the splitting increases with the difference of the anion radii. The relative size of the subbands strongly depends on the mixture ratio and on the thermal history. Each of the subbands gives its own fluorescence spectrum. As in pure crystals it consists of two subbands. The shorter wavelength band dominates at low temperatures. We interpret the results by considering complexes of the general form TlX_nY_6?n (n=1, ..., 5). Their symmetry is lower than in a uniform surrounding (n=0; 6). As a consequence the degeneracies of the excited electronic states are lifted. In KCl with a sufficient low content of KI we get only TlICl₅ in addition to TlCl₆. From the equilibrium at different temperatures we find 0.07 eV for the energy of association of I^? to Tl⁺. TlICl₅ centers absorb in theA ₀ band, which is equivalent to theA band of the pure TlCl₆, and in anA ₁ band at longer wavelength. TheA _n1 fluorescence can be linearly polarized up to 60% in [100] direction. By applying uniaxial stress to the crystal in [100] direction at higher temperatures the TlICl₅ complexes can be partially oriented parallel to [100]. This gives a slight dichroism in theA ₁ band.     

Inclusive electron production from heavy quarks in e+e− annihilation at 34.6 GeV center of mass energy

The production of electrons by bottom and charm hadrons has been studied in e⁺e^? annihilation at 34.6 GeV center of mass energy. It is observed that the b quark fragmentation function is peaked at large values of the scaling variable z with 〈z_b〉 = 0.84^{+0.15 + 0.15}_{?0.10 ? 0.11}. For c quarks 〈z_c〉 = 0.57^{+0.10 + 0.05}_{?0.09 ? 0.06} is observed. A forward-backward charge asymmetry of A = ?0.25 ± 0.22 was measured in b production.     

Optical absorption of s2-configuration ions in alkali halide crystals—III: The A band in Sn2+-doped crystals

The line shape of the A band in KCl:Sn²⁺, KBr:Sn²⁺, KI:Sn²⁺, RbCl:Sn²⁺ and RbBr:Sn²⁺ has been measured as a function of temperature between about 15 K and room temperature. As the spectra for all these systems are similar detailed results are presented only for RbCl: Sn²⁺, RbBr:Sn²⁺ and KBr: Sn²⁺. The experimental data resemble those of a previous study on KBr:In⁺ and KG:In⁺ in that the A band consists of two broad, overlapping components designated A₁ (the low energy component) and A₂. The separation between A₁ and A₂ is more marked at low temperature for Sn²⁺ than for In⁺, and no inversion of the ratio of the peak heights of A₁ and A₂ occurs as the temperature is varied, as was so for In⁺. Detailed calculations of the line shape are presented for KBr:Sn²⁺. These calculations show that one cannot account for the line shape purely in terms of the dynamical Jahn-Teller effect and that there is in addition a static splitting of the A state caused by a lowering in the symmetry of the crystal field.     

Parity violation in the 17/2− isomer of93Tc

The parity-violating mixing of the 17/2^? and 17/2⁺ levels in⁹³Tc nuclei, polarized by the tilted multifoil interaction, was measured by the observation of the forwardbackwardγ-ray asymmetry. The asymmetry was determined to beA _γ=1.18(48)×10^?3. The nuclear polarization was determined in a measurement of the quadrupole interaction in a⁹²Mo isomer and the parity violation matrix element 〈H _PV〉 is found to be ¦〈H _PV〉¦ =0.8(4) meV.     

Electronic spectra of potassium bromide containing thallium II. Emission spectrum excited at 2537 Å

The emission spectrum of KBr: Tl⁺ excited at 2537 Å has been measured in the temperature range 15–296°K. At low temperatures the spectrum consists of a prominent band at 4.01 eV, a much smaller band at 3.40 eV and a very small band at 3.15 eV. The last does not appear to change much with temperature and so could not be measured accurately. The temperature-dependence of the two main bands is complex. Between 60 and 100°K the low-energy band increases sharply in intensity, while the high-energy band decreases correspondingly. Above 110°K the situation reverses and the low-energy band decreases in intensity while the high-energy band grows. Both bands closely approximate symmetric Gaussians. The temperature-dependence of the intensity of these two bands is well-explained qualitatively by the existence of two kinds of minima on the adiabatic potential energy surface for the A state. However, predictions of the temperature-dependence of the two emission bands based on calculated adiabatic potential energy surfaces are not in quantitative agreement with the experimental results. Possible reasons for this are our lack of knowledge of precise values for the parameters which enter into the theory, namely the spin-orbit coupling constant, the exchange integral, and the electron lattice coupling constant. The possible role of the ³A_1u state in emission is discussed briefly.     

Mass content of ultrahigh-energy cosmic rays within different time periods

Estimates obtained for the average atomic number 〈lnA〉 of nuclei of primary particles with energies in the region of E ₀ ? 10¹⁵ eV over the past 36 years at the Yakutsk array and other arrays worldwide for studying extensive air showers are presented. It is shown that these estimates are markedly different with in different time periods. Earlier than 1996, the composition of cosmic rays in the energy range of 5 × 10¹⁵–10¹⁸ eV was markedly lighter than in later years. After 2008, there appeared a trend toward a decrease in 〈lnA〉. This is likely to be a manifestation of some explosive process in the Milky Way Galaxy after 1996.     

Thermomodulated A-band absorption of KBr: Tl

A marked oscillator-strength decrease of the A band in KBr: Tl has been pointed out by means of thermally-modulated optical measurements throughout the temperature range 88–380°K. The experimental results suggest the existence of a clear correlation between the states responsible of the absorption bands and are discussed in order to clarify the role of the thermal perturbation upon Tl⁺ energy levels.     

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.     

The origin of 3.55 eV emission band of RbCl:Tl

Fluorescence spectra of KCl:Tl, RbCl:Tl and NH₄Cl:Tl under A band excitation at room temperature (300 K) and liquid nitrogen temperature (77 K) have been re-examined in order to ascertain the origin of the 3.55 eV emission band of RbCl:Tl. The emission band at RT is found to show two components and the weaker component becomes dominant at LNT. The observations are explained in terms of Patterson's model of two local environments for Tl⁺ ion. One of them is a Tl⁺ having local CsCl like environment. The 3.55 eV emission band at 300 K is assigned to electronic transition in the Tl⁺ having local CsCl like environment.     

The interaction of oxygen with gadolinium: UPS and XPS studies

The interaction of oxygen with evaporated Gd films at 300 K has been studied for the first time using AlK α XPS and Hel and Hell UPS. The characteristic changes in the Gd(6s5d) and O(2p) valence bands, Gd(4f), Gd(5p) and Gd(4d) core levels, and O(2s) and O(1s) core levels were studied. Evidence is presented for the initial formation of an intermediate oxidation state at low exposure (characterized by a new Gd valence band with a maximum in the DOS at ～ 2.5 ev below E_F and an ～ 0.6 eV shift in Gd(4f)) prior to formation of Gd₂O₃ where the Gd(6s5d) valence band disappears completely, as expected for Gd³⁺. In the higher exposure range there is little further increase in the oxide thickness, which is estimated as $\text{? 20}\text{A}\text{?}$, but there is a slow replacement of O by OH, as characterized by a second O(1s) feature at 532.3 eV and OH 1π and 3σ orbitals in UPS at ～ 6.7 and 11.5 eV. The interpretations are supported by parallel studies on bulk Gd₂O₃ and by Ar⁺ sputtering experiments. Comparisons are made to other rare earth oxidation studies.     

Electron-lattice interaction in the absorption spectra of thallium doped alkali halides

The electron-lattice interaction of NaCl:Tl⁺, KCl:Tl⁺, KBr:Tl⁺, and KI:Tl⁺ is discussed using the moments of the absorption bands. The discussion is based on a theory ofToyozawa andInoue andHonma. Consistency of the data is found for the absorption measurements. An analysis of the band shift under applied stress shows for theA-band in KCl and KBr and for theA- andB-band in KI that the electronlattice coupling constants derived from these data assuming next neighbour interaction differ considerably from those derived from the second moments of the bands.     

Phase transition in RbNbWO6: The pyrochlore structure revisited

A transition from tetragonal to cubic symmetry has been observed in the pyrochlore RbNbWO₆ at ～ 120° C and is shown to be related to the Rb⁺ motion in the structure. A simple potential energy model is developed to study the motion of the A⁺ cation inside the framework (M₂X₆)^- of the pyrochlore structure : the site energy difference between the 16d and 8b positions is comparable to the experimental activation energy.