Fluoreszenzlebensdauern einiger wasserhaltiger Salze des Europiums und des Terbiums

At 300°K the fluorescent lifetimes of the levels⁵D₀ of Eu³⁺ and⁵D₄ of Tb³⁺ were measured in the RE(C₂H₅SO₄)₃·9H₂O, RE(BrO₃)₃·9H₂O, RECl₃·6H₂O, RE(NO₃)₃·6H₂O and (RE)₂(SO₄)₃·8H₂O. The fluorescent lifetimes of the above mentioned hydrated crystals are preliminary determined by radiationless transitions. An empirical relation can be obtained for the probabilityw for the radiationless transitions of the formw=const·α _RE·α _Lattice. The factorsα _RE andα _Lattice depend only on the rare-earth ion or the lattice respectively. A structure of the interaction Hamiltonian between the rare-earth ion and the lattice is proposed, which leads to the empirically found relation. The influence of electron- andX-irradiation on the lifetime of the level⁵D₄ in TbCl₃·6H₂O was investigated at 77°K. A decrease of the lifetime and a nonexponential decay of the fluorescence were found. By heating up the crystal to room temperature thermoluminescence and annealing of the irradiation defects are observed.     

Spectral-luminescent properties of Eu<Superscript>3+</Superscript> ions in inorganic D<Subscript>2</Subscript>O and POCl<Subscript>3</Subscript>-SnCl<Subscript>4</Subscript> solvents

Absorption and luminescence spectra of Eu³⁺ ions in D₂O and POCl₃-SnCl₄ inorganic solvents were measured. Oscillator strengths and spontaneous radiation transition probabilities for the most intense electron transitions in Eu³⁺ were calculated. Judd-Ofelt parameters, the radiative lifetime of the ⁵ D ₀ metastable level of Eu³⁺ in D₂O-Eu³⁺ and POCl₃-SnCl₄-Eu³⁺ solutions, and matrix elements for radiative transitions from the ⁵ D ₀ level were determined. The luminescence lifetime of the ⁵ D ₀ level of Eu³⁺ in these solutions was measured. The photoluminescence quantum yield for transitions from the ⁵ D ₀ level of Eu³⁺ in ⁵ D ₀ and POCl₃-SnCl₄-Eu³⁺ solutions was found to be 0.32 and 0.88, respectively.     

Optical spectra and emission characteristics of terbium-doped potassium–lead double chloride crystals (KPb<Subscript>2</Subscript>Cl<Subscript>5</Subscript>:Tb<Superscript>3+</Superscript>)

Optical transitions in KPb₂Cl₅:Tb³⁺ crystals are studied experimentally and theoretically. The absorption cross-section spectra are plotted and the oscillator strengths of transitions from the ground terbium state to excited multiplets are determined. Intensity parameters Ω_t for KPC:Tb³⁺ are determined by the Judd–Ofelt method to be Ω₂ = 2.70 × 10^–20 cm², Ω₄ = 7.0 × 10^–20 cm², and Ω₆ = 0.72 × 10^–20 cm². These values were used to calculate such characteristics of spontaneous radiative transitions as oscillator strengths, probabilities of radiative transitions, and radiative lifetimes. The emission spectra of KPb₂Cl₅:Tb³⁺ crystals upon UV excitation and the decay kinetics of luminescence from the excited ⁵ D ₃ and ⁵ D ₄ levels are studied experimentally, the lifetimes of these levels are determined, and the dependences of the rates of nonradiative relaxation from the excited ⁷ F _j (j = 0–5), ⁵ D ₄, and ⁵ D ₃ levels to lower-lying terbium levels are calculated. It is shown that the population of the ⁵ D ₄ level in KPC:Tb³⁺ crystals occurs according to a cascade scheme, which leads to quenching of the ⁵ D ₃ level. The calculated data agree well with the known experimental rates of multiphonon nonradiative transitions for Dy:KPC, Nd:KPC, Er:KPC, Tb:KPB, and Nd:KPB crystals. It is shown that transitions in the near-IR (3–6 μm) region in double halide crystals (MPb₂Hal₅) are almost unquenched and the rates of nonradiative relaxation of excited levels spaced by energy gaps ΔE _ji > 1000 cm^–1 are W _ji ^NR < 10³s^–1. This circumstance suggests that it is possible to obtain stimulated emission in KPb₂Cl₅:RE³⁺ crystals in the IR spectral region up to 6 μm.     

Laser spectroscopy of Eu<Superscript>3+</Superscript> cubic centers in the CaF<Subscript>2</Subscript> bulk single crystal

The optical transitions ⁵ D _{0, 1} → ⁷ F _J (J = 0, 1, ..., 6) of Eu³⁺ cubic centers in the CaF₂ single crystal are investigated using combined excitation and emission spectroscopy at different time delays after the excitation pulse. The energies of the Stark sublevels of the ⁷ F _J ground states are determined.     

Specific features of magneto-optical spectra of Tb<Subscript>3</Subscript>Ga<Subscript>5</Subscript>O<Subscript>12</Subscript>

The spectra of magnetic circular dichroism in the range of the ⁷ F ₆→⁵ D ₄ absorption band and the spectra of magnetic circular polarization of luminescence in the range of the ⁵ D ₄→⁷ F ₅ band in the terbium-gallium garnet Tb₃Ga₅O₁₂ are studied at a temperature of 80 K. The optical transitions between the Stark sublevels of the ⁷ F ₆, ⁷ F ₅, and ⁵ D ₄ multiplets are identified based on the analysis of the magneto-optical and optical spectra. It is shown that the experimentally determined symmetry and energy of the Stark sublevels of these multiplets confirm the results of numerical calculations of the energy spectrum of the Tb³⁺ rare-earth ion in terbium-gallium garnet.     

Optische Absorptionsspektren und Kristallfeldaufspaltungen des Er3+-Ions in YPO4 und YVO4

The optical absorption spectra of trivalent erbium in isostructural single crystals of YPO₄ and YVO₄ have been obtained between 14000 and 29000 cm^?1. The observed crystal field splittings are interpreted in terms of crystal potentials of symmetryD _2d. From the positions of 33 Stark components the five crystal field parametersB ₀ ² , B ₀ ⁴ , B ₀ ⁶ , B ₄ ⁴ andB ₄ ⁶ have been determined. The values of the parameters for Er³⁺:YPO₄ are significantly different from those of Er³⁺:YVO₄.     

Spectroscopy of optical centers of Eu<Superscript>3+</Superscript> ions in partially stabilized and stabilized zirconium crystals

The structure of the optical centers of Eu³⁺ ions in tetragonal (ZrO₂)_1–x–y (Y₂O₃) _x (Eu₂O₃) _y (х = 2.7–3.6; y = 0.1) and cubic (ZrO₂)_1–x–y (Y₂O₃) _x (Eu₂O₃) _y (х = 8–38; y = 0.1–0.5) crystals of solid solutions on the basis of zirconium dioxide is studied using the methods of optical and Raman-scattering spectroscopy. Characteristic optical centers of Eu³⁺ ions with different crystalline environments are revealed in the above compounds.     

Silica gel glasses with a high efficiency of luminescence sensitization in the Ce<Superscript>3+</Superscript>-Tb<Superscript>3+</Superscript> system

Terbium-and (Ce, Tb)-containing glasses prepared using the direct sol-gel-glass transition are studied. It is shown that glasses doped with one activator contain two main types of optical centers, namely, isolated and complex centers, which are characterized by weak and strong cross-relaxation quenching of luminescence from the ⁵D₃ state of Tb³⁺ ions, respectively. The Ce⁴⁺-Tb³⁺ (Tb⁴⁺) complex centers are formed during sintering of coactivated xerogels in oxygen and can be transformed into Ce³⁺-Tb³⁺ centers through saturation of the samples with hydrogen. The Ce³⁺-Tb³⁺ centers exhibit efficient luminescence from the ⁵D₄ state upon excitation into the absorption bands of Ce³⁺ ions.     

Zeeman effect and stark splitting of the electronic states of the rare-earth ion in the paramagnetic terbium garnets Tb<Subscript>3</Subscript>Ga<Subscript>5</Subscript>O<Subscript>12</Subscript> and Tb<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>

The Zeeman effect in the ⁷ F ₆ → ⁵ D ₄ absorption band of the Tb³⁺ ion in the paramagnetic garnets Tb₃Ga₅O₁₂ and Tb₃Al₅O₁₂ was studied. The field dependences of the Zeeman splitting of some absorption lines are found to exhibit unusual behavior: as the magnetic field increases, the band splitting decreases rather than increases. Symmetry analysis relates these lines to 4f → 4f electron transitions of the doublet-quasi-doublet or quasi-doublet-doublet type, for which the field dependences of the splitting differ radically from the well-known field dependences of the Zeeman splitting for quasi-doublet-quasi-doublet or quasi-doublet-singlet transitions in a longitudinal magnetic field.     

Sensitized luminescence of Eu and Tb macrocyclic complexes bearing benzophenone antennae

Sensitized luminescence behavior of lanthanide (Ln=Eu³⁺, Tb³⁺) macrocyclic cyclen (1,4,7,10-tetraazacyclododecane) complexes bearing one or four benzophenone (BP) moieties as antenna (LnL1 and LnL4) has been studied in water. Despite higher molar extinction coefficient of EuL4 owing to four antennae, it shows only one-thirtieth the luminescence intensity of EuL1. Energy level of triplet excited-state of BP antenna (E_T) is only a few kJ mol⁻¹ higher than that of ⁵D₂ excited-state of Eu³⁺, thus promoting a back energy transfer (BET) from ⁵D₂ of Eu³⁺ to ground-state BP antennae. On EuL4 bearing four antennae, BET occurs more rapidly than that on EuL1, thus exhibiting much weaker luminescence. For Tb complexes, the energy gap between E_T of BP antenna and ⁵D₄ excited state of Tb³⁺ is large enough (>13 kJ mol⁻¹), such that practically no BET occurs. The luminescence intensity of TbL4 is, however, lower (two-third) than that of TbL1. Time-resolved luminescence measurement reveals that hydration number of Tb³⁺ within TbL4 is twice that within TbL1. This is because the structural distortion of ligands on TbL4, caused by an intramolecular dipole-dipole interaction among the BP antennae, allows coordination of higher number of H₂O molecules to Tb³⁺, thus leading to a strong Tb luminescence quenching via O-H oscillators.     

Photoluminescence of Ca(Al<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ga<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>2</Subscript>S<Subscript>4</Subscript>:Eu<Superscript>2+</Superscript> compounds

Photoluminescence (PL) observed in solid solutions of Ca(Al _x Ga_1–x )₂S₄:Eu²⁺ (x = 0.1–0.3) is studied. It is shown that the increase in emission intensity by 18% is caused by changes in the x values and electronic 5d → 4 f transitions in Eu²⁺ ions. A change in the position of the emission spectrum or its partial shift toward shorter wavelengths is due to an increase in the aluminum concentration and a decrease in the crystal field energy. The energy of the zero phonon line E ₀, redshift D, and the Stokes shift ΔS are determined. A decrease in the photoluminescence intensity maximum and an increase in the half-width of the spectrum are found in the temperature range of 10–300 K. The efficiency of emission at temperatures of 20 and 300 K is almost independent of the excitation power density of up to ~10⁴ W/cm². The luminescence lifetime of Eu²⁺ ions was 383, 357, 346, and 333 ns for x = 0, 0.1, 0.2, and 0.3, respectively.     

Polarisationseffekte in der Hyperfeinstruktur von65Cu I, 3d 94s 2 m 2 D

The hyperfinestructure of the transition⁶⁵CuI, 3d ¹⁰4p ² P _3/2—3d ⁹4s ² m ² D _5/2 was investigated by optical interferometric methods. For the hfs-factors the following values were found:A(⁶⁵Cu,m ² D _5/2)=26,79(3) mK andB(⁶⁵Cu,m ² D _5/2)=5,81(10) mK. The core polarization of them ² D-terms and the Sternheimer corrections in the calculation of the quadrupolmoment of copper 65 from theB-factors of the terms 3d ⁹ 4s² m ² D and 3d ¹⁰ 4p ² P _3/2. were discussed.     

Spectral and luminescence properties of gadolinium gallium garnet epitaxial films doped with terbium

Gadolinium gallium garnet single-crystal films containing terbium are grown through liquid-phase epitaxy from a supercooled solution melt in the PbO-B₂O₃ system. The optical absorption spectra in the wavelength range 0.2–10.0 μm and the luminescence spectra excited by synchrotron radiation with energies in the range 3.5–30.0 eV are investigated at temperatures of 10 and 300 K. It is revealed that the optical absorption spectra contain an absorption band with the maximum at a wavelength λ ≈0.260 μm, which corresponds to the spin-allowed electric dipole transition between the electronic configurations 4f ⁸(⁷ F ₆) → 4f ⁷(⁸ S)5d of the Tb³⁺ ions. The narrow low-intensity absorption bands attributed to the 4f → 4f transitions from the ⁷ F ₆ ground level to the ⁷ F _0–5 multiplet levels of the Tb³⁺ ions are observed in the wavelength range 1.7–10.0 μm. In the luminescence spectra measured at a temperature of 10 K, the highest intensity is observed for a band with the maximum at a wavelength λ ≈ 0.544 μm, which is associated with the ⁵ D ₄ → ⁷ F ₅ radiative transition in the Tb³⁺ ion.     

Zeitliches Abklingen und Anisotropie von p-Terphenyl- undp-Terphenyl-Anthrazen-Mischkristallen bei Beschuß mit α-Teilchen

The time dependence of scintillation intensity from single crystals ofp-terphenyl and mixed crystals ofp-terphenyl and anthracene after bombarding with α-particles was investigated at the two temperaturesT=296 °K andT=92 °K. For the crystals ofp-terphenyl the time dependence of the scintillation anisotropy was also measured. Using the formulas given byKing andVoltz the decay curves ofp-terphenyl were decomposed into two components. Good agreement between experiment and theory was found. The ratio of the prompt intensity to the delayed intensity was determined to be 1∶2 atT=296 °K and 1∶3 atT=92 °K. The diffusion constants for triplet excitons were calculated to beD _T(296 °K)≈10^?5 cm² sec^?1 andD _T(92 °K)≈ 2×10^?6 cm² sec^?1, and the triplet-triplet interaction rate constantsχ _tt(296 °K)≈ 2.5×10^?11 cm³ sec^?1 andχ _tt(92 °K)≈0.5×10^?11 cm³ sec^?1.     

Paramagnetische Resonanz von Er3+ in Y2O3

The paramagnetic resonance absorption of trivalent erbium in single crystals of Y₂O₃ on sites of crystal field symmetry C_3i and C₂ is investigated at 4.2°K and 9.2 kMc/s. The values of theg-tensors and those of the hyperfine structure parallel to the axes of crystalline fields are:g _‖=12.176,g _⊥=3.319,A=426.4·10^?4 cm^?1, andg _z =12.314,g _x =1.645,g _y =4.892, andA _z =433.2·10^?4 cm^?1 for the C_3i-ions and the C₂-ions, respectively. For ions on sites of symmetry C₂ the principal axes ofg in the plane perpendicular toz are found ± 2° beside the [100]-directions. This is different from the result on Yb³⁺ in Y₂O₃. The dependency ofg on the angle of rotation is determined for the (001)-, (110)-, and (111)-plane.     

Zur Frage des Grundzustandes im Tb I-Spektrum

In an atomic beam magnetic resonance experiment on Tb¹⁵⁹ ΔF=0 transitions in several hfs-levels of thermally excited fine structure states have been observed. Detailed analysis of data showed twoJ=15/2 states, oneJ=13/2, oneJ=11/2, and, probably, oneJ=9/2 state to be present. For these levelsg _J-values are given. It was concluded that the ground state of neutral terbium is 4f ⁸ 5d 6s ^{2 8} G _15/2. The 4f ⁹ 6s ^{2 6} H _15/2-level lies not more than 1000 cm^?1 higher.     

Europium luminescence in fluorite upon high-energy excitation

The reflection and luminescence excitation spectra of CaF₂ crystals containing europium ions in divalent (Eu²⁺) and trivalent (Eu³⁺) states were measured in the range from 4 to 16 eV. It was established that, in CaF₂ : Eu³⁺ crystals, luminescence of Eu³⁺ ions (the f-f transitions) is effectively excited both in the charge-transfer band (at ～8 eV) and in the region of the 4f–5d transitions (at ～10 eV) but is virtually not excited in the fundamental region of the crystal (at an energy higher than 10.5 eV). Luminescence of Eu²⁺ ions (the 427-nm band) in CaF₂ : Eu³⁺ is effectively excited in the fundamental region of the crystal; i.e., luminescence of divalent europium ions occurs through the trapping mechanism. Emission of Eu²⁺ ions in CaF₂ : Eu²⁺ crystals is characterized by the excitation band at an energy of 5.6 eV (the 4f → 5d,t _2g transitions), as well as by the exciton and interband luminescence excitations. The results obtained and data available in the literature are used to construct the energy level diagram with the basic electron transitions in the CaF₂ : Eu crystals.     

Die Hyperfeinstruktur in den 4f7 6s 6p-Termen des Eu I und die elektrischen Kernquadrupolmomente von Eu151 und Eu153

The hyperfine structure of the statesz ¹⁰ P _11/2,z ¹⁰ P _9/2,z ¹⁰ P _7/2,z ⁸ P _9/2,y ⁸ P _9/2,y ⁸ P _7/2,y ⁸ P _5/2,z ⁶ P _7/2,z ⁶ 6s P _5/2 of the 4f ⁷ 6p configuration of EuI was investigated with a photoelectric recording Fabry Perot spectrometer using enriched isotopes of Eu¹⁵¹ and Eu¹⁵³, which have been excited in liquid air cooled hollow cathodes. From the measurements the values for the nuclear quadrupole moments

$$Q(Eu^{151} ) = (1.16 \pm 0.08) \cdot 10^{ - 24} cm^2 $$     

Hyperfeinstruktur im HolmiumÄthylsulfat

In holmium ethylsulfate diluted with lanthanum ethylsulfate we have investigated the transition⁵ I ₈→F ₅ at 4,2 ?K using a combination of a Fabry-Pérot-interferometer and a high resolution grating spectograph. The hyperfine structure splitting of four lines was resolved; the hyperfine structure parameters for the two lowest crystal field levels of the⁵ I ₈ groundterm were determined.     

Zur Chronologie des alten Ägypten

The velocityv of the propagation of discharge along the anode of a self-quenchingG—M-counter is a function of total pressureP, pressure of the quenching gasP _D, radius of the cathoder _a and of the anoder _i andV _ü the difference between working- and starting-potential. For the mixtures argon-methylal, argon-alcohol and helium-alcohol isv=v ₀·exp[k·(V _ü/V _e)^1/2] withv ₀ the velocity at the starting potentialV _e v ₀=(a+b·P _D/P)·V _n ^1/2 ·exp [(c?d·P_D/P·V _n ^?1/2 ] andV _n=V _e·(lnr _a/r _i)^?1.k, a, b, c andd are characteristical constants of the filling gas.