Measurement of hyperfine structure and isotope shifts in the 580.56nm line of 142－145,146,148,150Nd+

Isotope shifts and hyperfine spectrum of singly ionized neodymium ion was measured by collinear fast-ion-beam laser spectroscopy. The hyperfine A constants and B constants are obtained for the (23230)9/2^0 level and 4f^45d ^6K9/2 level, respectively. The optical isotope shifts between seven isotopes in the 580.56 nm of^142-145,146,148,150Nd^ line are determined. The configuration admixtures for (23230)9/2^0 level were quantitatively analysed to be 4f^46p, 4f^35d^2, and 4f^35d6p with mixing coefficients of 67%, 5%, and 28%, respectively.     

STUDY OF HIGH-LYING EXCITED STATES OF RARE-EARTH ELEMENT Dy BY LASER RESONANCE IONIZATION SPECTROSCOPY

This paper describes the investigation of high-excited states of Dy. which includes the measurement of high Rydberg states and autoionizing states, by means of laser resonance ionization spectroscopy (LRIS). Two high Rydberg series (n>40), 4f¹⁰(⁵I₈) 6sns and 4f¹⁰(⁵I₈) 6snd, have been obtained by exciting the state of 4f¹⁰(⁵I₈) 6s6p (³P⁰₂) ⁵I⁰₈ using two-step laser excitation-electric field ionization method. With the data obtained, we determined the first ionization potential of Dy. It is 47901.7±0.6 cm^-1, that is. about one order more accurate than the results given in the literature. Using the same technique, we found 97 autoionizing states by exciting the state of 4f⁹5d6s(⁷H⁰₇).     

Excited states in124Xe

The isomer shift in the optical transition Eu II 4f⁷(⁸S ₇ ^2/o )⁶p_3/2 ^(7/2,3/2)4?4f⁷ (⁸S ₇ ^2/o )5d⁹D ₄ ^o , λ=6O4.95 nm, has been measured between the isotope^152gEu(3^?) and its isomer^152mEu(0^?). From the valuev(^152gEu)–v(^152mEu)=736(10) MHz the deformation parameter of^152mEu has been estimated to be^152mβ?+0.25. This value is smaller than^152gβ as obtained from isotope shift measurements and the spectroscopic quadrupole moment. The influence of the shape difference on the decay of^152mEu is discussed.     

Structures and thermochemistry of methyl ethyl sulfide and its hydroperoxides: HOOCH2SCH2CH3, CH3SCH(OOH)CH3, CH3SCH2CH2OOH,and radicals

Hydroperoxides and the corresponding peroxy radicals are important intermediates during the partial oxidation of methyl ethyl sulfide (CH₃SCH₂CH₃) in both atmospheric chemistry and in combustion. Structural parameters, internal rotor potentials, bond dissociation energies, and thermochemical properties (ΔH_f^o, S^o and C_p(T)) of 3 corresponding hydroperoxides CH₂(OOH)SCH₂CH₃, CH₃SCH(OOH)CH₃, CH₃SCH₂CH₂OOH of methyl ethyl sulfides, and the radicals formed via loss of a hydrogen atom are important to understanding the oxidation reactions of MES. The lowest energy molecular structures were identified using the density functional B3LYP/6‐311G(2d,d,p) level of theory. Standard enthalpies of formation (ΔH_f^o₂₉₈) for the radicals and their parent molecules were calculated using the density functional B3LYP/6‐31G(d,p), B3LYP/6‐31 + G(2d,p), and the composite CBS‐QB3 ab initio methods. Isodesmic reactions were used to determine ?H_f^o values. Internal rotation potential energy diagrams and rotation barriers were investigated using the B3LYP/6‐31G(d,p) level theory. Contributions for S^o₂₉₈ and C_p(T) were calculated using the rigid rotor harmonic oscillator approximation based on the structures and vibrational frequencies obtained by the density functional calculations, with contributions from torsion frequencies replaced by internal rotor contributions. The recommended values for enthalpies of formation of the most stable conformers of CH₃SCH₂CH_2, CH₂(OOH)SCH₂CH₃, CH₃SCH(OOH)CH₃, and CH₃SCH₂CH₂OOH are ?14.0, ?33.0, ?37.2, and ?32.7 kcal/mol, respectively. Group additivity values were developed for estimating properties of structurally similar and larger sulfur‐containing peroxides. Groups for use in group additivity estimation of sulfur peroxide thermochemical properties were developed.     

NEW AUTOIONIZING STATES NEAR THE FIRST IONIZATION LIMIT OF RARE EARTH ELEMENT Dy

This paper describes the investigation of autoionizing states near the first ionization limit of rare-earth element Dy. The 62, 51, 97 and 25 new autoionizing states resulting from the states of 4f¹⁰(⁵I₈)6s6p(³P⁰₂)³I⁰₇, 4f⁹ (⁶H⁰)5d²(³F)(⁸G⁰)6s⁹G⁰₇, 4f⁹(⁶F⁰)5d6s^{2 7}H⁰₇ and 4f⁹5d6s^{2 7}K⁰₇, respectively, were found by using a laser resonance ionization time-of-flight mass spectrometer (LRI-TOFMS), The photoionization efficiencies for different channels were compared with each other. In addition, the Shore-Fano parameters of autoionizing states were determined by a nonlinear fitting program.     

Photo- and radio-excited luminescence properties of Eu-doped La2O3–Al2O3 based eutectics

Eutectic crystal of 0.5% Eu-doped 30LaAlO₃–70Al₂O₃ (vol %) was prepared by micro-pulling down (μ-PD) technique under nitrogen atmosphere. Being excited at a wavelength of 320 nm, the crystal exhibited intense emission band with a maximum at 450 nm which is corresponding to 4f⁶5d-4f⁷(⁸S_7/2) transitions of Eu²⁺. The decay time and fluorescence quantum efficiency (QE) were determined to be about 475 ns and 60%, respectively. When alpha-ray excited the crystal, both Eu²⁺ 4f⁶5d-4f⁷(⁸S_7/2) and Eu³⁺ 4f⁶-4f⁶ (⁵D₀-⁷F_1,2) emission peaks were observed at 435 nm and 600 nm. By the pulse height spectra, the relative scintillation light yield of the crystal was about 4% compared with that of BGO commercial scintillator.     

Experimental Study and Modelling of Formation and Decay of Active Species in an Oxygen Discharge

A microwave (2.45 GHz) oxygen discharge (3 hPa, 150 W, 50 mL.min^–1) is studied by optical emission spectroscopy of O(⁵P) (line 777.4 nm) and of the atmospheric system of O₂(head‐line 759.4 nm). Calibration of the spectral response of the optical setup is used to determine the concentrations of O(⁵P) and O₂(b). The concentration of the O(⁵P) atoms is in the range 108–109 cm^–3 and the concentration of the O₂(b) molecules is in the range 10¹⁴ – 2 × 10¹⁴ cm^–3 along the discharge tube. An attempt is made to simulate the experimental results by using coupling the Boltzmann equation, homogeneous energy transfer V‐V and V‐T, heterogeneous reactions on the walls (energy transfer and recombination of atoms) and a kinetic scheme (electronic transfer and chemical reactions). The Boltzmann equation includes momentum transfer, inelastic and superelastic processes and e‐e collisions. V‐V and V‐T transfer equations are obtained from the SSH theory and the kinetic scheme includes 65 reactions with 17 species [electrons e, ions O^– and O₂^–, fundamental electronic neutral species O(³P), O₂, O₂(X,v), O₃ and excited neutral species O₂(a), O₂(b), O₂(A), O(¹D), O(¹S), O(⁵P), O(4d ⁵D^o), O(5s ⁵S^o), O(3d ⁵D^o) and O(4s ⁵S^o)]. A fair agreement between experimental results and modelling is obtained with the following set of fitting values: – heterogeneous deactivation coefficient for O₂(b) γ = 2.6 × 10^–2; – rate constant of reaction [O(¹D) + O(³P) → 2 O(³P)] k₃₄ = 1.4 × 10^–11 cm³.s^–1; – electron concentration in the range 10¹⁰ – 10¹¹ cm^–3. Modelling shows that the recombination coefficient for oxygen atoms on the silica wall (range 1.4 × 10^–3 – 0.2 × 10^–3) is of the same order as the values obtained in a previous paper and that the ratio ([O] / 2 [O₂]initial) is about 33–50%. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Isotopic shifts and the hyperfine structure of the samarium spectral lines at 672 and 686 nm

Spectra of saturated absorption of Sm atomic vapor from the ground state ⁷ F ₀ and the first even metastable level ⁷ F ₁, ε′=292.58 cm^?1 of the 4f ⁶6s ² configuration to the odd level 4_f ⁶(⁷ F)6s6p(³ P ^o)⁹ F ₁ ^o , ε,=14863.85 cm^?1 were recorded. The lines of the isotopic series were identified, and the hyperfine structure of lines in the spectra of isotopes with a nonzero nuclear spin was determined. The relative isotopic shifts and the hyperfine splitting of the even level 4f ⁶6s ²(⁷ F ₁) were determined.     

The study of two-color excitation upconversion of Pr(0.5)Yb(3):ZBLAN

The excited state absorption upconversion of Pr(0.5)Yb(3):ZBLAN glass material, under two-color excitation of the 960 nm semiconductor laser and the Xe lamp light simultaneously, is reported in this article. It was found that the upconversion emission spectra of 480.1, 519.0, 601.9 and 631.8 nm coincide with the common emission spectra. Meanwhile, the upconversion-excitation spectrum has three obvious peaks under two-color excitation, and they respectively correspond to the 856.0 nm upconversion excitation transition [¹G₄(Pr³⁺)→¹I₆(Pr³⁺) and ¹G₄(Pr³⁺)→³P₁(Pr³⁺)], the 789.0 nm upconversion excitation transition ¹G₄(Pr³⁺)→³P₂(Pr³⁺), and the 803.7 nm upconversion excitation transition ³H₆(Pr³⁺)→¹D₂(Pr³⁺). The upconversion excitation transition ¹G₄(Pr³⁺)→¹I₆(Pr³⁺) is strong because its oscillator strength f = 23.040×10⁻⁶ is large, which results in a large peak appearing in the upconversion excitation spectrum. That is just the new interesting two-color excitation upconversion luminescence phenomenon of Pr(0.5)Yb(3):ZBLAN induced by one laser and one continuous normal light simultaneously.     

Simultaneous generation of violet,blue, and green lasers using Nd:YAl3(BO3)4 channel waveguides under pumping at 815 nm

Violet, blue, and green lasers were simultaneously generated by nonlinear processes using ultrafast laser inscribed neodymium‐doped yttrium aluminum borate (Nd:YAl₃(BO₃)₄ or Nd:YAB) channel waveguides under pumping at 815 nm. These visible lasers were generated by the frequency doubling, self‐frequency summing, and self‐frequency doubling processes based on a 1062 nm laser radiation that corresponded to the ⁴F_3/2 → ⁴I_11/2 transition of Nd³⁺ ions. Further, the wavelength tunability for the violet and blue lasers was achieved by simply tuning the pump wavelength within the ⁴I_9/2 → ⁴F_5/2 transition. The results obtained indicate that Nd:YAB waveguides are promising candidates for efficient compact visible laser sources. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

OPTICAL ISOTOPE SHIFTS AND CONFIGURATION MIXING AT THE LEVEL (26772)011/2 IN Nd II

Optical isotope shifts in the transition 4f⁴5d ⁶I_11/2-(26772)⁰_11/2 of Nd II were measured by using collinear fast-ion-beam laser spectroscopy. The configuration admixtures of the previously unclassified (26772)⁰_11/2 level were quantitatively analyzed to be 4f⁴6p, 4f³5d², and 4f³5d6s with mixing probabilities of 13%, 85%, 2%, respectively.     

Determination of isotope shift crossed-second-order-effects and hyperfine-structure parameters in the Eu I configuration 4f 7 6s7s

In the Eu I configuration 4f ⁷(⁸ S)6s7s the isotope shift (IS) and hyperfine-structure (hfs) of the levelse ⁸ S _7/2 andf ⁸ S _7/2 were determined from the transitions 684.5 nm, 733.7 nm and 821.0 nm to 4f ⁷6s6p. Together with experimental results of our previous measurements a theoretical analysis of the IS and hfs for the complete configuration 4f ⁷ 6s7s can now be carried out. From the IS of the four 6s7s-levels we evaluated the two crossed-second-order-parametersg ₃(4f,6s)= ?l.l(l)mK andg ₃(4f, 7s)= ?0.1(l)mK. The ratiog ₃/G ₃ is determined for various Eu configurations and found to be equal to 5.6(3)·10^?6 in complete agreement with a theoretical value following from Hartree-Fock calculations. The single electron hfs splitting constantsa ¹⁰(4f)= ?1.9 (3) mK,a ¹⁰(6s)=396(3)mK, anda ¹⁰(7s)=65(3)mK are also determined and compared with those of other Eu configurations.     

Oscillator strength measurements of the 4s5s 3S1 → 4snp 3Po2 Rydberg transitions of zinc

In the present experimental work, oscillator strengths of the 4s5s ³S₁ → 4snp ³P^o₂ (18?≤?n?≤?53) Rydberg transitions of zinc are reported. The stepwise laser excitation from the ground state 4s^{2 1}S₀ was achieved using three dye laser beams simultaneously pumped by the second (532?nm) and third (355?nm) harmonics of a Q-switched Nd: YAG (Neodymium-doped yttrium aluminum garnet) laser. The vapor containment and detection system was a single wire thermionic diode ion detector operating in space charge limited mode. A trend of the above-mentioned f-values from n?=?18 to 53 versus the principle quantum number n has been presented. Furthermore, continuity has been verified between the discrete f-values and the oscillator strength density at the threshold.     

Vacuum ultraviolet 5d14f9-4f10 emission of Ho3+ ions in alkaline-earth fluorides

Time-resolved emission and excitation spectra as well as emission decay kinetics of CaF₂, SrF₂, BaF₂ doped with HoF₃ were investigated. Intensive emission bands near 168 nm, having long decay time, are caused by the spin-forbidden transitions from the 5d¹4f⁹ high-spin states to the ground ⁵I₈ states of Ho³⁺ ions. Weak spin allowed 5d¹4f⁹(low-spin)-4f¹⁰ emission band at 158 nm was observed only in CaF₂–Ho crystals. Spin allowed and spin-forbidden excitation bands were observed near 166 and 155 nm, respectively, in all studied crystals. Fast component of spin-forbidden emissions due to multiphonon relaxation to low-lying 4f¹⁰ Ho³⁺ level also was observed for all crystals.     

Quantum Effect on the Energy Levels of Eu2+ Doped K2Ca2(SO4)3 Nanoparticles

Quantum confinement effect on the energy levels of Eu²⁺ doped K₂Ca₂(SO₄)₃ nanoparticles has been observed. The broad photoluminescence (PL) emission band of Eu²⁺ doped K₂Ca₂(SO₄)₃ microcrystalline sample observed at ～436 nm is found to split into two narrow well resolved bands, located at 422 and 445 nm in the nanostructure form of this material. This has been attributed to the reduction in the crystal field strength of the nanomaterials, which results in widening the energy band gap and splitting the broad 4f⁶5d energy level of Eu²⁺. Energy band gap values of the micro and nanocrystalline K₂Ca₂(SO₄)₃ samples were also determined by measuring the UV–visible absorption spectra. These values are 3.34 and 3.44 eV for the micro and nanocrystalline samples, respectively. These remarkable results suggest that activators having wide emission bands might be subjected to weak crystal strength via nanostructure materials to modify their electronic transitions. This might prove a powerful technique for producing new-advanced materials for use in the fields of solid state lasers and optoelectronic devises.     

Spectral structure of barium–phosphate–silicate phosphor Ba10(PO4)4(SiO4)2:EuM+

The new apatite–silicate phosphor doped with Eu ions in Ba₁₀(PO₄)₄(SiO₄)₂ matrix was synthesized through solid-state reaction. It was found that the as-synthesized phosphor displayed apparent mixture of band and line emission peaks giving rise to pseudo white light. The narrow emission bands peaking at 410 nm can be assigned to the 4f⁶5d→4f⁷(⁸S_7/2) transition of Eu²⁺ ions, and the other band at 507 nm is ascribed to anomalous fluorescent emission. One group of line emission peaking at 595 nm and 613 m were due to the ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transition of Eu³⁺ ions. The occurrence of photostimulated luminescence and discrete emission lines in violet (410 nm), green (507 nm) and red (595 nm and 613 nm) colors indicate that this material has potential application in fields of white-light-emitting.     

Dimer radical cation of 4‐thiouracil: a pulse radiolysis and theoretical study

Pulse radiolysis with optical absorption detection has been used to study the reactions of hydroxyl radical (OH^?) with 4‐thiouracil (4TU) in aqueous medium. The transient absorption spectrum for the reaction of OH^? with 4TU is characterized by λ_max 460 nm at pH 7. A second‐order rate constant k_(4TU+OH) of 1.7 × 10¹⁰ M^?1 s^?1 is determined via competition kinetics method. The transient is envisaged as a dimer radical cation [4TU]₂^?+, formed via the reaction of an initially formed radical cation [4TU]^?+ with another 4TU. The formation constant of [4TU]₂^?+ is 1.8 × 10⁴ M^?1. The reactions of dibromine radical ion (Br₂^??) at pH 7, dichlorine radical ion (Cl₂^??) at pH 1, and azide radical (N₃^?) at pH 7 with 4TU have also produced transient with λ_max 460 nm. Density functional theory (DFT) studies at BHandHLYP/6–311 + G(d,p) level in aqueous phase showed that [4TU]₂^?+ is characterized by a two‐centerthree electron (2c‐3e) [?S∴S?] bond. The interaction energy of [?S∴S?] bond in [4TU]₂^?+ is ?13.01 kcal mol^?1. The predicted λ_max 457 nm by using the time‐dependent DFT method for [4TU]₂^?+ is in agreement with experimental λ_max. Theoretical calculations also predicted that compared with [4TU]₂^?+, 4‐thiouridine dimer is more stable, whereas 4‐thiothymine dimer is less stable. Copyright © 2013 John Wiley & Sons, Ltd.     

Visible superfluorescence from optically pumped europium atoms

We have observed superfluorescence (SF) on five atomic transitions at visible wavelengths 633.58, 635.00, 640.09, 640.61 and 736.22 nm in Doppler broadened gas of europium (Eu) atom. The nanosecond SF pulses were observed by longitudinally pumping Eu vapor column with a pulsed dye laser to upper states 4f⁶5d6s², ⁸D_7/2at 346.79 nm and 4f⁷5d6p, ¹⁰F_5/2at 348.73 nm from the ground state 4f⁷6s², ⁸S_7/2. High optical conversion efficiency ≈10% was measured for these SF transitions. Our experiment deals with the large sample multilevel SF in the regime where the length of the excited column L is greater than the maximum value of the Arecchi-Courtens length (L_c). The observed variation of SF peak intensity (I_fl) and time delay for SF evolution (τ_D) with number of atoms in the excited state (N) resemble theoretically predicted SF scaling laws for transverse excitation, namely I_fl∝N and t_D μ 1/?N\tau_D \propto 1/{\sqrt N} although the experimental condition is similar to the swept excitation. This could be due to the Rabi frequency associated with the pump transition which is comparable to the SF delay time precluding the initiation of SF at different times along the sample and results in transverse (instantaneous) excitation. The experimental τ_D values were found to be in agreement with the quantum mechanical calculations describing SF.     

Optical Analysis of Er3+:Boro-Fluoro-Phosphate Glasses

This paper deals with the preparation and optical analysis of Er³⁺ (0.2 mol%) boro-fluoro-phosphate glasses in the following glass compositions:

• Series A: 69.8 B₂O₃–10 P₂O₅–10(ZnO/CdO/TeO₂)–10 AlF₃

• Series B: 69.8 B₂O₃–10 P₂O₅–10(ZnO/CdO/TeO₂)–10 LiF

Measured Vis-NIR absorption spectra of Er³⁺:boro-fluoro-phosphate glasses have revealed nine absorption bands at 377 nm, 405 nm, 450 nm, 486 nm, 519 nm, 543 nm, 649 nm, 973 nm and 1529 nm, which correspond with the transitions of ⁴I_15/2 → ⁴G_11/2, (²G_9/2,⁴H_9/2), ⁴F_5/2, ⁴F_7/2, ²H_11/2, ⁴S_3/2, ⁴F_9/2, ⁴I_11/2, and ⁴I_13/2, respectively. With an excitation at λ _exci = 375 nm, a bright green emission (⁴S_3/2 → ⁴I_15/2) at 547 nm has been observed from these erbium glasses. Judd–Ofelt characteristic intensity Ω_λ (λ = 2, 4, 6) parameters are obtained from the absorption spectra, and these results were used to compute the radiative properties of Er³⁺:boro-fluoro-phosphate glasses. The NIR emission (⁴I_13/2 → ⁴I_15/2) at 1547 nm from these glasses was measured with an Ar⁺ laser (514.5 nm) as an excitation source.     

Blue laser cooling transitions in Tm I

We have studied possible candidates for laser cooling transitions in ¹⁶⁹Tm in the spectral region of 410–420 nm. By means of saturation absorption spectroscopy, we have measured the hyperfine structure and rates of two nearly closed cycling transitions from the ground state 4f¹³6s²(²F₀)(J_g=7/2) to upper states 4f¹²(³H₅)5d_3/26s²(J_e=9/2) at 410.6 nm and 4f¹²(³F₄)5d_5/26s²(J_e=9/2) at 420.4 nm and evaluated the life times of the excited levels as 15.9(8) ns and 48(6) ns, respectively. Decay rates from these levels to neighboring opposite-parity levels are evaluated by means of Hartree–Fock calculations. We conclude that the strong transition at 410.6 nm has an optical leak rate of less then 2×10^-5 and can be used for efficient laser cooling of ¹⁶⁹Tm from a thermal atomic beam. The hyperfine structure of two other even-parity levels, which can be excited from the ground state at 409.5 nm and 418.9 nm, is also measured by the same technique. In addition, we give a calculated value of 7(2) s^-1 for the rate of magnetic-dipole transition at 1.14 μm between the fine structure levels (J_g=7/2)↔(J’_g=5/2) of the ground state which can be considered as a candidate for applications in atomic clocks. PACS 32.70.Cs; 32.10.Fn; 32.80.Pj