An optical study of the stretching absorption band near 3 microns from OH- defects in LiNbO3

A near infrared absorption band (λ = 2.87 μ), identified as the 0–1 stretching vibrational band of OH^- defects in LiNbO₃, has been observed at 6, 77, and 300 K. This band was completely polarized perpendicular to the crystallographic c-axis within experimental error and two peaks, separated by approximately 13 cm^?1, were resolved. Both the structure and optical anisotropy of this band were independent of stoichiometry and sample treatments and may be understood in terms of a simple model where protons are captured by O^2- anions forming OH^- defects whose orientations are determined by neighboring O^2- ions.     

Atmospheric chemistry of diazomethane – an experimental and theoretical study

The kinetics of the O₃, OH and NO₃ radical reactions with diazomethane were studied in smog chamber experiments employing long-path FTIR and PTR-ToF-MS detection. The rate coefficients were determined to be k _CH2NN+O3?=?(3.2?±?0.4)?×?10^?17 and k _CH2NN+OH?=?(1.68?±?0.12)?×?10^?10 cm³ molecule^?1 s^?1 at 295?±?3?K and 1013?±?30 hPa, whereas the CH₂NN?+?NO₃ reaction was too fast to be determined in the static smog chamber experiments. Formaldehyde was the sole product observed in all the reactions. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ calculations showing the reactions to proceed exclusively via addition to the carbon atom. The atmospheric fate of diazomethane is discussed.     

Spin-spin interaction of Dy3+ ions in KY(WO4)2

The spin-spin interaction of Dy³⁺ ions in a KY(WO₄)₂ single crystal is investigated by electron paramagnetic resonance (EPR) spectroscopy at a temperature of 4.2 K and a frequency of 9.2 GHz. The EPR spectra of ion pairs located in different coordination shells are analyzed. It is revealed that the considerable contribution to the spin-spin interaction of the nearest neighbor ion pair nn is made not only by the magnetic dipole-dipole interaction but also by the isotropic exchange interaction with the parameter I _nn = (+601 ± 17) × 10^?4cm^?1. The exchange interaction in pairs of more widely spaced ions is substantially weaker: I _5n = (?38 ± 3) × 10^?4cm^?1 and I _9n = (+18 ± 4) × 10^?4cm^?1. For the other ion pairs, the magnetic dipole-dipole interaction dominates. It is found that the EPR spectra of single ions and ion pairs exhibit a superhyperfine structure associated with tungsten nuclei.     

The measurements of correlation times of molecules adsorbed on silica gel,alumina and charcoal using NOESY and MAS NMR

The correlation times (τ_c) and cross relaxation rates of toluene, dimethylformamide, tetrahydrofuran, water-acetone and water-dioxane adsorbed on silica gel, alumina and charcoal were obtained by measurements of the integrated intensities of cross and diagonal peaks in their NOESY spectra. The (τ_c) of the above mentioned systems is in the range of 10^?6?10^?9 s, much longer than that in the liquid (10^?12?10^?14 s). It was found that intramolecular rotation of toluene adsorbed on charcoal is slower than that on SiO₂, Al₂O₃ and the inversion of α and β protons in tetrahydrofuran is very fast (τ_c = 1.76×10^?9 s). The cross relaxation plays an important role in the relaxation of molecules adsorbed on solid surfaces with low electron densities.     

Oxygen ion conduction in 12CaO·7Al2O3: O2− conduction mechanism and possibility of O− fast conduction

12CaO·7Al₂O₃ (C12A7) with a unique nano-porous structure and free O^2? ions entrapped in sub-nanometer-sized cages is a fast oxygen-ion-conducting material. These free O^2– may be replaced by various oxygen-related species, OH^?, O^2? and O^?, by tuning the atmosphere during the heat treatment. We examined the conduction mechanism for stoichiometric C12A7 (C12A7:O^2?), in which O^2? ions exist as counter anions in sub-nanometer-sized cages, by Raman measurement of C12A7:O^2? annealed in a dry ¹⁸O₂ atmosphere. It was revealed that the primary ion conducting species is an O^2? ion which diffuses via exchange with O^2? in the cage wall. An experimental result on the sample containing O^? ions implied that O^? is more mobile than O^2? in C12A7. Ab initio calculations on the diffusion paths of O^2? and O^? ions in C12A7 supported the above experimental results.     

Optical and luminescence properties of Dy3+ ions in K–Sr–Al phosphate glasses for yellow laser applications

Trivalent dysprosium (Dy³⁺)-doped K–Sr–Al phosphate glasses have been prepared and investigated for their optical and luminescence properties. Judd–Ofelt theory has been used to derive radiative properties for the ⁴F_9/2 level of Dy³⁺ ions. The luminescence spectrum of 1.0 mol% Dy₂O₃-doped glass shows intense yellow emission around 572 nm ascribed to ⁴F_9/2 → ⁶H_13/2 transition with 78 % branching ratio and emission cross section of the order of 2.48 × 10^?21 cm². Moreover, the quantum efficiency of the ⁴F_9/2 level has been found to be 76 %. The luminescence decay curves for the yellow emission (⁴F_9/2 → ⁶H_13/2) have been measured and analyzed as a function of Dy³⁺ ion concentration. The results revealed that Dy³⁺-doped phosphate glasses could be useful for yellow laser applications.     

On the bound states in the muonic molecular ions

Absolute cross sections for electron impact ionization and dissociation of OH⁺ and OD⁺ leading to the formation of the OH²⁺, O⁺, O²⁺, O³⁺ and D⁺ ions have been measured by applying the animated electron-ion beam method in the energy range from the respective reaction thresholds up to 2.5 keV. The maximum of the single ionization cross section is found to be (0.95? ± ?0.02) × 10^?19 cm² at 155 eV. The maximum total cross sections for O⁺ and D⁺ fragments production are observed to be (15.7? ± ?0.2) × 10^?17 cm² at 95 eV and (10.8? ± ?0.5) × 10^?17 cm² at 95 eV, respectively. The cross sections for O²⁺ and O³⁺ are much smaller, (5.37? ± ?0.04) × 10^-18 cm² at 135 eV and (7.95? ± ? 0.23) × 10^-20 cm² at 315 eV, respectively. The collected data are analyzed in details in order to determine separately the contributions of dissociative excitation and of dissociative ionization to the O⁺ and D⁺ fragments production.     

Temperature dependence of Mn2+ EPR in Sn2P2S6 near the phase transition

The X-band EPR spectrum of Mn²⁺ in Sn₂P₂S₆ was studied in the temperature rangeT=223–363 K. At room temperature the spin-Hamiltonian constants areg=2.00±0.01,B ₂ ⁰ =(163±3)·10^?4 cm^?1,B ₂ ² =(159±3)·10^?4 cm^?1,A=?(75±1)·10^?4 cm^?1. The effect of the invariance in temperature of the resonance magnetic fields in the narrow temperature rangeT=337–340 K and the model of the paramagnetic centre are discussed. According to EPR data a phase transition occurs atT=337 K. This transition from the paraelectric phase to the ferroelectric one is accompanied by a dramatic change in value of the spin-Hamiltonian constantB ₂ ⁰ .     

Negative Ions,Ozone, and Metastable Components in dc Oxygen Glow Discharge

In a dc glow discharge in oxygen, the concentrations of minor components of O₂(a¹Δ_g), O₂(b¹ Σ_g), O₃, O(¹D), as well as nagative ions and electrons have been measured. Balance equations have been derived which describe satisfactorily the stationary concentrations of these components as functions of gas pressure and discharge current. For the first time, the rate constants of important aeronomical reactions (a) O^? + O₂(a¹Δ_g) → O₃ + e, (b) O₂^? + O₂(a¹Δ_g) → 2O₂ + e and (c) e + O₃ → O₂^? +O have been measured as functions of gas temperature T and mean energies of ions E_i and electron E₆: K_a = (2.5 ± 0.5) · 10^?9 · (T/300)^{4 ± 0.4}· (E_i/0.04)^{?2.6 ± 0.4} cm³/s for T = 385?605 K and E_i = 0.10 ? 0.66 eV; K_b = (1.0 ± 0.3) · 10^?10 · (T/300)^{?2 ± 0.5} · (E_i/0.04)^{0.23 ± 0.05} cm³/s for T = 330?605 K and E_i = 0.09 + 1.5 eV; K_c for E_e = 0.8÷5 eV.     

Heat capacity of oxides in the Bi2O3-SiO2 system

The high-temperature heat capacity of Bi₄Si₃O₁₂, Bi₂SiO₅, and Bi₁₂SiO₂₀ has been investigated. It has been found that there is a correlation between the specific heat C _p ⁰ (298 K) and the composition of oxides in the Bi₂O₃-SiO₂ system.     

Der Zerfall des Tb158m

Tb^158m was produced from Tb¹⁵⁹ by (n, 2n) reaction and investigated using scintillation spectrometers. The following results were obtained: half-life\(T_{\tfrac{1}{2}} = (10.5 \pm 0.2)\) sec; energy of the isomeric transitionE _γ =(109.9±1.4) keV; conversion coefficients α _K =56±3; α _L +α _M +?=50±8; α_total=106±10;K/L-ratioK/L=1.3±0.3, yielding the multipole order of the isomeric transition to beM3. Upper limits for the direct beta transitions from the isomeric state to the ground states of the neighbouring even-even nuclei Gd¹⁵⁸ and Dy¹⁵⁸ are 10^?4 and 6·10^?3, respectively.     

Effect of 100 MeV swift Si8+ ions on structural and thermoluminescence properties of Y2O3:Dy3+nanophosphor

Nanoparticles of Y₂O₃:Dy³⁺ were prepared by the solution combustion method. The X-ray diffraction pattern of the 900°C annealed sample shows a cubic structure and the average crystallite size was found to be 31.49?nm. The field emission scanning electron microscopy image of the 900°C annealed sample shows well-separated spherical shape particles and the average particle size is found to be in a range 40?nm. Pellets of Y₂O₃:Dy³⁺ were irradiated with 100?MeV swift Si⁸⁺ ions for the fluence range of 3?×?10^11_3?×?10¹³ ions cm^?2. Pristine Y₂O₃:Dy³⁺ shows seven Raman modes with peaks at 129, 160, 330, 376, 434, 467 and 590?cm^?1. The intensity of these modes decreases with an increase in ion fluence. A well-resolved thermoluminescence glow with peaks at ～414?K (T_m1) and ～614?K (T_m2) were observed in Si⁸⁺ ion-irradiated samples. It is found that glow peak intensity at 414?K increases with an increase in the dopant concentration up to 0.6?mol% and then decreases with an increase in dopant concentration. The high-temperature glow peak (614?K) intensity linearly increases with an increase in ion fluence. The broad TL glow curves were deconvoluted using the glow curve deconvoluted method and kinetic parameters were calculated using the general order kinetic equation.     

Study of K^ - \to \pi ^0 e^ - \overline \nu _e \gamma decay with ISTRA+ setup

Results of study of the $K^ - \to \pi ^0 e^ - \overline \nu \gamma $ decay at the ISTRA+ setup are presented. We observed 4476 events of this decay. The branching ratio is found to be $R = \frac{{Br(K^ - \to \pi ^0 e^ - \overline \nu _e \gamma )}}{{Br(K^ - \to \pi ^0 e^ - \overline \nu _e )}}$ = (1.81±0.03(stat.)±0.07(syst.)) × 10^?2 for E*_γ > 10 MeV and θ*_eγ > 10°. For comparison with the previous experiment the branching ratio with cuts E*_γ > 10 MeV, 0.6 < cos θ*_eγ < 0.9 is calculated: R = $\frac{{Br(K^ - \to \pi ^0 e^ - \overline \nu _e \gamma )}}{{Br(K^ - \to \pi ^0 e^ - \overline \nu _e )}}$ = (0.47±0.02(stat.) ± 0.03(syst.)) × 10^?2. For the cuts E*_γ > 30 MeV and θ*_eγ > 20°, used in most theoretical papers, Br = (3.06 ± 0.09(stat.) ± 0.14(syst.)) × 10^?4. For the asymmetry we get A _ξ = ?0.015 ± 0.021. At present it is the best estimate of this asymmetry.     

Properties of Hg implanted Hg1−x Cd x Te infrared detectors

Experimental performance parameters of Hg implanted Hg_1?x Cd _x Te photovoltaic detectors are analyzed. At 77K, for 8–14 μm band, a comparison is made between performances and theoretical ultimate diffusion limits in low frequency direct detection. Experimental features are well-explained by a model based on the Auger band-to-band process for carrier recombination. Peak detectivities exceeding 10¹¹ cm Hz^1/2W^?1, external quantum efficiencies as high as 90%, and zero-bias resistance-area products better than 1 Ω·cm² have been achieved in devices with 12 μm cutoff wavelengths. In the 3–5 μm band performances are far from the diffusion limit. Notwithstanding, at 77K zero-bias resistance-area products are better than 10⁴Ω·cm² and detectivities of the order of 10¹² cm Hz^1/2W^?1 were observed at 5 μm. Predominant generation-recombination contribution are present at room temperature in 1–1.3 μm photodiodes whose detectivities, primarily limited by the Johnson noise, at 1.3 μm are higher than 10¹¹ cm Hz^1/2W^?1 at 300 K. The high frequency response of the photodiodes is also discussed. Response times as low as 0.5 ns are reached despite some limitations arising from the implanted layer sheet resistance.     

Critical behaviour of a uniaxial ferromagnet,ErCl3·6H2O with predominant dipolar interactions

The parallel magnetic susceptibility χ of a uniaxial ferromagnet ErCl₃·6H₂O has been measured between 0.3 and 4.2K and specially near T_c = 0.353 K. The predominant contribution to the Curie-Weiss temperature is due to the dipolar interactions. χ is proportional to ?^?γ with $\text{? =}\text{T}\text{T}{}_{\mathrm{c}}\text{?1}$ in the range 10^?3 < ? < 5 × 10^?2. The γ value, γ = 1.01 ±0.03 is consistent with the theoretical prediction for a uniaxial dipolar ferromagnet.     

Optical waveguides in LiNbO3 formed by ion implantation

Abstract

Ion implantation in LiNbO₃ can be used to modify the refractive index. The change in indices, n ₀ n _e results from the damage formed by energy deposited by the (dE/dx)_nuclear collisions between the ions and the lattice and is independent of the ion species. A saturation change in index of some ?7% occurs after a deposition of 10²³ keV cm^?3 at 300K, greater changes of ?9 % occur with implants at 77K. Annealing studies indicate the optical absorption formed during irradiation is removed below 200°C whereas the index changes exist up to 400°C. For optical waveguide production a negative change in the index is not ideal as the damaged layer cannot directly act as the region of optical confinement. However the (dE/dx)_electronic term is unimportant and so we have been able to form optical waveguides by ion implantation with light energetic ions (e.g. MeV He⁺ ions) because the damaged layer is then formed beneath an unchanged high index surface layer. This retains the desirable electrooptic properties of the single crystal LiNbO₃. The experimentally observed waveguide modes are in accord with our theoretical predictions of the refractive index profiles.     

Single-crystalline M-type Sr Hexaferrites studied by <Superscript>57</Superscript>Fe Mössbauer spectroscopy

The ⁵⁷Fe Mössbauer spectra of the single crystalline and the finely ground Sr_1?x La _x Fe_12?y Co _y O₁₉ (x = 0 : y = 0, x = 0.192 : y = 0.152 and x = 0.456 : y = 0.225) samples have been measured to investigate the La-Co substitution effects. All observed spectra at 150 K were well fitted using the five subspectra which correspond to the five crystallographical nonequivalent Fe sites in the M-type hexaferrite, indicating that the valence changes to Fe²⁺ ions in the Fe³⁺ ions were not observed in our Sr_1?x La _x Fe_12?y Co _y O₁₉ samples. In SrFe₁₂O₁₉, the relative absorption intensities in the five subspectra show the large anisotropies in the recoilless fractions at the five Fe sites whereas these anisotropies were not observed in Sr_0.544La_0.456Fe_11.775Co_0.225O₁₉. These results indicate the chemical compositional dependence on the anisotropies of the recoilless fractions at the five Fe sites. The substitution of a Co²⁺ ion for the Fe³⁺ ion changes the center shifts of the Fe³⁺ ions near the Co²⁺ ion by the perturbation of the Fe-O-Co hybridizations. Therefore, the Co²⁺ ions occupy the 4f ₁ and the 4f ₂ sites due to the chemical compositional dependences of the refined magnetic hyperfine field and center shifts of the Fe³⁺ ions.     

Spurenanalyse von Cu in ZnS-Phosphoren mittels Neutronenaktivierung

The half life of the 206 kev state of Re¹⁸⁷ was determined with delayed coincidence technic to be:T _1/2=(5·70±0·05)·10^?7 s. The rotation of the spin of the 206 kev state in a magnetic field has been observed in a differential angular correlation measurement with the 480 kev?72 kevγ?γ cascade. From the observed Larmor frequency a magnetic moment ofμ=(5·02±0·06)μ _K for the 206 kev level has been derived. The 480 kev?72 kevγ?γ angular correlation was found to be undisturbed in an aqueous solution of ammoniumtungstate.     

Spins und γ-Multipolordnungen beim Zerfall Fe59→Co59

In the decay of Fe⁵⁹ the following quantities have been measured:γ-ray intensities, conversion coefficients andβ-(circularly polarizedγ) correlations. The conversion coefficients were found to be: for the 1.10 MeVγ-transition, α_tot.=(1.36±0.10)·10^?4 and for the 1.29 MeVγ-transition, α_tot.=(1.07±0.08)·10^?4. The asymmetry parameterA of the correlationβ(0.27 MeV)?γ(1.29 MeV) were measured to beA= ?0.17±0.10, and forβ(0.46 MeV)?γ(1.10 MeV),A=?0.13±0.04. From these data and publishedγ?γ angular correlation measurements the following spins of Co⁵⁹ levels could be deduced: 1.10 MeV,I=5/2^?; 1.29 MeV,I=5/2^?; and 1.43 MeV,I=3/2^?. The two strongβ-ray groups are pure Gamow-Teller transitions (ΔI=1). The multipolarities of all fiveγ-rays are given.     

Structures of proton solvates in the HCl-H2O-(CH3)2NCHO system as determined by IR spectroscopy and quantum-chemical calculations

The structures of proton solvates in the HCl-H₂O-(CH₃)₂NCHO (DMFA) system at H₂O: DMFA ratios ranging from 1: 1 to 21: 1 are studied by the IR spectroscopy method. It is demonstrated that H₂O?H⁺?OH₂ ions and (CH₃)₂NCHO?H⁺?OH₂ mixed solvates with a strong quasi-symmetrical hydrogen bond are formed in solutions. With an increase in the DMFA concentration, the fraction of H₅O ₂ ⁺ ions decreases. At HCl: H₂O ≥ 1: 3 and arbitrary DMFA concentrations, only mixed proton solvates are formed. The continuous absorption coefficients for the (CH₃)₂NCHO?H⁺?OH₂ ions are determined. The results obtained are compared with the results of quantum-chemical calculations of the structure and relative stability of the (DMFA) _m H⁺(H₂O) _n (m = 0–2, n = 0–3) positively charged complexes which were performed by the B3LYP/6-31++G(d,p) DFT method. We identified 19 stable configurations with chain, cyclic, and branched structures. Most of these configurations contain the (CH₃)₂NCHO?H⁺?OH₂ fragment. The parameters of the O?H⁺?O bridge show that some configurations have a strong quasi-symmetrical hydrogen bond. In some cases, the proton is located between two DMFA molecules. The H₂O?H⁺?OH₂ bridge is observed in none of the stable configurations of the (DMFA) _m H⁺(H₂O) _n (m ≠ 0) complexes.