Pu3体系的结构与势能函数

用相对论有效原子实势(RECP)和密度泛函(B3LYP)方法对Pu_n(n=2,3)体系的结构进行了优化,得到了Pu₂和Pu₃分子的几何构型分别为D_∞h,D_3h,其基态分别为13和19重态.在B3LYP/RECP水平上得到Pu₂分子的光谱常数ω_e=52.3845cm^-1,ω_e　χ_e=0.02 关键词： 2')" href="#">Pu₂ 3')" href="#">Pu₃ 分析势能函数     

Internal irradiation effects in239Pu doped K2Ca2(SO4)3): EPR,TSL and PAS investigations

The electron/hole trapped centres created during internal irradiation in²³⁹Pu doped K₂Ca₂(SO₄)₃ were investigated using electron paramagnetic resonance (EPR), thermally stimulated luminescence (TSL) and photoacoustic spectroscopic studies (PAS). These techniques were used to identify the defects and characterize the thermally induced relaxation processes. TSL studies of self (α)/γ-irradiated²³⁹Pu doped K₂Ca₂(SO₄)₃ revealed two glow peaks around 400 and 433K. Plutonium introduced as Pu⁴⁺ was partly reduced to Pu³⁺ due to self irradiation. This was ascertained from PAS studies. EPR studies carried out on these samples showed the formation of radical ions SO ₄ ⁻ , SO ₃ ⁻ , O ₃ ⁻ , etc. The thermal destruction of SO ₄ ⁻ ion was found to be associated with the prominent glow peak around 433K. Pu³⁺ was found to act as luminescent centre for the observed TSL glow. The trap depth for the glow peak at 433K has been determined from TSL and EPR data.     

First-principles local density approximation （LDA）＋U and generalized gradient approximation （GGA） ＋ U studies of plutonium oxides

The electronic structures and properties of PuO2 and Pu2O3 have been studied according to the first principles by using the all-electron projector-augmented-wave （PAW） method. The local density approximation （LDA）＋U and the generalized gradient approximation （GGA）＋U formalisms have been used to account for the strong on-site Coulomb repulsion among the localized Pu 5f electrons. We discuss how the properties of PuO2 and Pu2O3 are affected by choosing the values of U and exchange-correlation potential. Also, the oxidation reaction of Pu2O3, leading to the formation of PuO2, and its dependence on U and exchange-correlation potential have been studied. Our results show that by choosing an appropriate U it is possible to consistently describe structural, electronic, and thermodynamic properties of PuO2 and Pu2O3, which enable the modelling of the redox process involving Pu-based materials.     

The Possibility of the Use of Coprecipitation with Lanthanum Fluoride for Preparation of Samples for Alpha-Spectrometric Determination of Plutonium

At present time the content of ²³⁹Pu, ²³⁸Pu especially in biological and environmental samples and nuclear fuels is frequently determinated. After radiochemical separation is plutonium usually electrodeposited on a metallic disk [1, 2]. Alpha-activity is then detected by silicon surface barrier detector.

The method of electrodeposition shows several disadvantages. The solution to be electrolyzed must have a definite composition, certain elements, e.g. iron, must not be present. The method is rather time-consuming and requires special equipment. Several other methods for preparation of samples using coprecipitations [3] or inorganic ionexchangers [4] have been studied. In this work was investigated the possibility of the use of coprecipitation of Pu³⁺ with LaF₃ for preparation of samples for alpha-speetroinetric determination of plutonium.     

Characterization and photoluminescence properties of some MLn2(1−x)O4:2xEu or 2xTb systems (M=Ba or Sr, Ln=Gd or La)

BaGd₂O₄, BaLa₂O₄ and SrLa₂O₄ powders doped with different concentrations of Eu³⁺ or Tb³⁺ are prepared by combustion synthesis method and the samples were further heated to 500, 700 and 900 °C to improve the crystallinity of the materials. The structure and morphology of materials have been examined by X-ray diffraction and scanning electron microscopy. It is remarkable that all the samples of BaGd₂O₄, BaLa₂O₄ and SrLa₂O₄ have similar morphology. The SEM images show homogeneous aggregates of varying shapes and sizes, which are composed of a large number of small elliptical shaped crystallites with an average diameter of about 0.5-3.0 μm. Photoluminescence for all materials increases with increase of temperature and shows a maximum for the samples heated to 900 °C with 4 mole% doping of Eu³⁺ or Tb³⁺ ions. The luminescence is almost same for all powders when doped with same concentration of Eu³⁺.     

Persistent luminescence — Quo vadis?

The present status of the persistent luminescence mechanisms is reviewed and the remaining unsolved details are discussed. These details include the identification and role of defects in the Eu²⁺-doped and R³⁺ co-doped alkaline earth aluminates (MAl₂O₄) and disilicates (M₂MgSi₂O₇; M:Ca, Sr, Ba) which can be partly resolved by the thermoluminescence (TL) measurements. The use of the synchrotron radiation - presently only sparsely used in the studies of persistent luminescence - is introduced: the oxidation state of the presumed R²⁺/R³⁺/R^IV species occurring in the persistent luminescence materials during the luminescence processes were examined with synchrotron radiation XANES (and EXAFS) methods. The band gap energies (E_g), the defect-related luminescence as well as the 4f⁷→4f⁶5d¹ transition energies were derived from the synchrotron radiation excitation spectra of the materials. Subsequently, the early steps of the density functional theory (DFT) calculations involving the solution of the persistent luminescence mechanisms (band gap energies, position of the Eu²⁺ levels) are discussed. Some remaining challenges are eventually highlighted.     

Structural and spectroscopic properties of small Pun （n= 2-5） molecules

The equilibrium structures and the electronic, spectroscopic and thermodynamic properties of small Pu_n (n=2-5) molecules are systematically investigated using the methods of general gradient approximation (GGA) of density functional theory (DFT). The results show that the bond length of the lowest-energy structure of Pu₂ is 2.578 AA. The ground state structure of Pu₃ is a triangle with D_3h symmetry, whereas for Pu₄, the ground state structure is a square (D_4h) and the spin polarization of 16 for molecule Pu₅ with square geometry (D_4h) is the most stable structure. For the ground state structures, the vibrational spectra as well as thermodynamic parameters are worked out. In addition, the values for the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) along with the energy gap of all the Pu_2-5 structures are presented. The relevant structural and chemical stabilities are predicted.     

Luminescence of transparent glass ceramics containing Er<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript> zirconate-titanate nanocrystals

Luminescence regularities have been studied in new erbium/ytterbium materials based on glasses and glass ceramics of a magnesium-aluminosilicate system containing nanoscale erbium/ytterbium zirconate titanate crystals with the pyrochlore structure. Lifetimes of Yb³⁺ and Er³⁺ ions in the ² F_5/2 state and in the ⁴I_11/2 and ⁴I_13/2 states, respectively, and the efficiency of Yb³⁺ → Er³⁺ energy transfer have been evaluated. The identified spectral-luminescent characteristics of the studied glasses and glass ceramics co-doped with erbium and ytterbium ions show that these materials are promising media for producing laser generation in the spectral range around 1.5 μm.     

Effect of annealing in vacuum on the magnetic anisotropy of Ag-doped CdCr2Se4 crystals

Angular dependences of resonance field and linewidth have been measured for ferromagnetic CdCr₂Se₄ crystal doped with 1.5 mol.% Ag before and after annealing in vacuum. The change of the sign of anisotropy due to annealing is associated with transformations Cr⁴⁺→Cr³⁺→Cr²⁺. On the basis of obtained data some suppositions are made about the mechanisms of conductivity in the Ag-doped CdCr₂Se₄ crystal.     

Rare earth ions (Eu3+ and Nd3+) doped BaSnF4: transport and photoluminescence characteristics

Investigation on the X-ray diffraction results of rare earth ions such as Eu³⁺ and Nd³⁺ doped BaSnF₄ materials indicates that the doped materials show a similar pattern of BaSnF₄ with the same tetragonal structure (P₄/nmm). The transport properties of the materials have been investigated by impedance spectroscopy, and the results show that the conductivity values are closely related to both concentration and type of the dopant ion. All of these doped materials show an increase in conductivity over un-doped BaSnF₄. The highest conductivity is observed in 3 mol% Nd³⁺ ion-doped BaSnF₄ system (9.01?×?10^?4 Scm^?1), which is about one order higher in comparison to BaSnF₄ conductivity (1.1?×?10^?4 Scm^?1). The room temperature emission spectrum of BaSnF₄:Eu³⁺ and BaSnF₄:Nd³⁺ shows the characteristic bands arising from ⁵D₀?→?⁷F _j (j?=?1, 2, 3, and 4) and ⁴F_3/2 to ⁴I _j (j?=?9/2 and 11/2) transitions of Eu³⁺ and Nd³⁺ ions, respectively.     

A survey of phosphors novel for thermography

With regard to phosphor thermometry, seven luminescent ceramic materials were synthesised and characterised, namely CaMoO₄:Eu³⁺, CaTiO₃:Pr³⁺, LaPO₄:Eu³⁺, LaVO₄:Eu³⁺, LiAl₅O₈:Fe³⁺, TiMg₂O₄:Mn⁴⁺ and ZnGa₂O₄:Mn²⁺. In this context, emission spectra and temperature lifetime characteristics are presented. Thus, a survey of phosphors novel for thermography is given in order to encourage further studies and more detailed characterisations of the respective materials.     

Electron-density distribution and physical properties of plutonium-gallium alloys: Ab initio cluster calculations

A cluster model based on ab initio density-functional theory was used to model gallium-stabilized δ-plutonium alloys, and to calculate the electron-density distribution, its pressure dependence, bond lengths, elastic properties (second order and third order), and inelastic properties for Pu₁₂Ga (7.7 at% Ga) and Pu₁₈Ga (5.3 at% Ga). The electron distribution was found to contain localized, semi localized, and delocalized contributions, with the second possessing covalent character. Two of plutonium’s 8 valence electrons were found to be itinerant, consistent with a recent prediction based on an electrostatic model, with the electron configuration for plutonium being 7s^0.57p^0.55f¹ (itinerant) and 6d¹5f⁵ (localized), and that for gallium being 4s¹4p². Applied hydrostatic pressure shifts the charge density toward a more localized Pu(d)-based distribution. The onset of the pressure-induced δ-Pu to α-Pu phase change is accompanied by a ∼0.2 electron increase in the localized population that may serve as a driving force for the phase change. Interior bonding within the Pu₁₂Ga subunits is stronger than that of the surrounding plutonium lattice, and the Pu-Ga bonds therein relax in a direction opposite to lattice strain. This study predicts covalency in metallic plutonium, both in the Pu-Ga bonding and in the Pu-Pu bonding.     

Thermally stimulated luminescence and electron paramagnetic resonance studies of actinide doped calcium chloro phosphate

Electron paramagnetic resonance [EPR] and thermally stimulated luminescence [TSL] studies were conducted on self [α]-irradiated²³⁹Pu doped calcium chloro phosphate andγ-irradiated²³⁹Pu/²³⁸UO ₂ ²⁺ doped calcium chloro phosphate to elucidate the role of the electron/hole traps in thermally stimulated reactions and to obtain trap parameters from both TSL and EPR data. TSL glow peaks around 135 K (# peak 1), 190 K (# peak 2), 435 K (# peak 5) and 490 K (# peak 7) were observed and their spectral characteristics have shown that Pu³⁺ and UO ₆ ⁶⁻ act as luminescent centres in calcium chloro phosphate with respective dopants. EPR studies have shown the formation of the radical ions H⁰, PO ₄ ²⁻ , O⁻, O ₂ ⁻ and [ClO]²⁻ under different conditions. Whereas the [ClO]²⁻ radical being stable up to 700 K, was not found to have any role in TSL processes, the thermal destruction of other centres was found to be primarily responsible for the TSL peaks observed. The trap depth values were determined both by using the TSL data and also the temperature variation of EPR spectra of these centres.     

Density functional study of Pu<Subscript>2</Subscript>C<Subscript>3</Subscript>

The structural, magnetic, electronic, vibrational, thermodynamic and elastic properties of plutonium sesquicarbide (Pu₂C₃) are investigated based on density functional theory. The use of the Hubbard term to describe the 5f electrons of plutonium is discussed according the lattice parameters and magnetism. The calculated lattice constants, magnetism and density of states agree well with the experimental data or other theoretical calculations. The Pu-C bonds of Pu₂C₃ have a mixture of covalent character and ionic character, while covalent character is stronger than ionic character. The phonon frequencies and the assignment of infrared-active, Raman-active and silent modes at Γ point are obtained. Furthermore, the enthalpy difference H-H₂₉₈, entropy S, heat capacity and linear thermal expansion coefficient α of Pu₂C₃ have been calculated and compared with the available data. Lastly, the calculated elastic properties predict that Pu₂C₃ is ductile metal. In addition, the effect of spin-orbit coupling on the structural, magnetic, and electronic properties of Pu₂C₃ has been discussed. We hope that our results can provide a useful reference for further theoretical and experimental research on Pu₂C₃.     

Unusual luminescence of octahedrally coordinated divalent europium ion in Cs2MP2O7 (M=Ca, Sr)

The excitation and emission spectra of octahedrally coordinated europium ion (Eu²⁺) ions in Cs₂M²⁺P₂O₇ (M²⁺=Ca, Sr) are reported and discussed. The remarkable features of the Eu²⁺ luminescence in these phosphate materials include (a) very large Stokes shift of emission (∼1 eV), (b) high luminescence quenching temperature, and (c) unusually low energy of the emitted photons for Eu²⁺ luminescence in phosphate-based materials. The broad emission bands of Eu²⁺ in Cs₂CaP₂O₇ and Cs₂SrP₂O₇ peak at 607 and 563 nm, respectively. The Stokes shift, crystal field splitting, centroid shift and the red shift of the Eu²⁺ 4f⁶5d¹ electronic configuration have been estimated from the relevant optical data. The radiative lifetime of the Eu²⁺ emission in Cs₂M²⁺P₂O₇ is ∼1.2 μs. The nature of the Eu²⁺ emission in Cs₂M²⁺P₂O₇ is discussed and arguments are presented to associate the luminescence with an extreme case of normal 4f⁶5d¹→4f⁷[⁸S_7/2] emission.     

The effect of Y co-doping on the persistent up-conversion luminescence of the ZrO2:Yb,Er nanomaterials

The effect of the defects due to the charge compensation obtained with the yttrium co-doping to the ZrO₂:Yb³⁺,Er³⁺ up-converting phosphors was studied. The materials were prepared with the combustion method. The materials purity was analyzed with the FT-IR spectroscopy. The crystal structure was studied with the X-ray powder diffraction and the crystallite sizes were estimated with the Scherrer formula. Up-conversion luminescence was excited at room temperature with an IR-laser at 970 nm. The up-conversion luminescence spectra showed red (650-685 nm) and green emission (520-560 nm) due to the ⁴F_9/2→⁴I_15/2 and (²H_11/2,⁴S_3/2)→⁴I_15/2 transitions of Er³⁺, respectively. Persistent up-conversion luminescence was observed both in the Yb³⁺,Er³⁺ and Y³⁺,Yb³⁺,Er³⁺ doped materials.     

Synthesis, characterization and upconversion emission properties of the nanocrystals of Yb/Er-codoped YF3-YOF-Y2O3 system

Nanocrystalline Yb³⁺, Er³⁺-codoped fluoride (YF₃), oxyfluoride (YOF), and oxide (Y₂O₃) phosphors have been synthesized by a facile pyrolysis of a yttrium trifluoroacetate precursor. YF₃, YOF and Y₂O₃ nanoparticles were demonstrated to be good host materials for lanthanides. Varied hosts led to different optical properties. Red, green, and blue up-conversion (UC) was observed upon excitation in the NIR spectral range in all synthesized compounds. The UC mechanisms were also analyzed.     

共沉淀法制备Y2SiO5∶Er3+ ,Yb3+ ,Tm3+及其上转换发光性能研究

采用化学共沉淀法制备了系列Y_1.98-2xYb_2x Er_0.02SiO₅(0.00≤x≤0.15)以及Y_1.736Yb_0.24Er_0.02Tm_0.004SiO₅上转换发光材料,比较了室温下Y_1.98-2xYb_2x Er_0.02 SiO₅ (x=0.00,0.08)样品在400—1600 nm范围内的吸收光谱,测量了所有样品在976 nm OPO激光器激发下的上转换发射光谱,以及Er³⁺离子⁴S_3/2(⁴F_9/2)→⁴I_15/2,Tm³⁺离子¹G₄→³H₆荧光衰减曲线和不同激发功率下的上转换蓝光发射强度,从而分析讨论了Er³⁺,Tm³⁺在Y₂SiO₅中的上转换发光机理.研究结果表明:在1250 ℃相对较低的温度下合成了X2型单斜晶系Y₂SiO₅ ∶Ln³⁺(Ln³⁺=Er³⁺,Yb³⁺,Tm³⁺),Yb³⁺的敏化显著增强了样品在976 nm附近的吸收能力,并大幅度加宽了该处的吸收带.分析上转换发射光谱发现:上转换绿光和红光强度都随着Yb³⁺浓度的增加先增强后减弱,但红光的猝灭浓度较高,归因于Er³⁺→Yb³⁺反向能量传递ETU4和Yb³⁺→Er³⁺正向能量传递ETU3过程的发生;上转换蓝光发射是三光子吸收过程,是通过Yb³⁺,Tm³⁺之间三次声子辅助的能量转移方式实现的. 关键词： 上转换 共沉淀 2SiO₅∶Er³⁺')" href="#">Y₂SiO₅∶Er³⁺ 3+')" href="#">Yb³⁺ 3+')" href="#">Tm³⁺     

Synthesis and luminescence properties of YVO4:Eu,Bi phosphor with enhanced photoluminescence by Bi doping

YVO₄:Eu³⁺,Bi³⁺ phosphors have been prepared by the high-temperature solid-state (HT) method and the Pechini-type sol-gel (SG) method. Spherical SiO₂ particles have been further coated with YVO₄:Eu³⁺,Bi³⁺ phosphor layers by the Pechini-type SG process, and it leads to the formation of core-shell structured SiO₂/YVO₄:Eu³⁺,Bi³⁺ phosphors. Therefore, the phase formations, structures, morphologies, and photoluminescence properties of the three types of as-prepared YVO₄:Eu³⁺,Bi³⁺ phosphors were studied in detail. The average diameters for the phosphor particles are 2-4 μm for HT method, 0.1-0.4 μm for SG method, and 0.5 μm for core-shell structured SiO₂/YVO₄:Eu³⁺,Bi³⁺ particles, respectively. Photoluminescence spectra show that effective energy transfer takes place between Bi³⁺ and Eu³⁺ ions in each type of as-prepared YVO₄:Eu³⁺,Bi³⁺ phosphors. Introduction of Bi³⁺ into YVO₄:Eu³⁺ leads to the shift of excitation band to the long-wavelength region, thus the emission intensities of ⁵D₀-⁷F₂ electric dipole transition of Eu³⁺ at 615 nm upon 365 nm excitation increases sharply, which makes this phosphor a suitable red-emitting materials that can be pumped with near-UV light emitting diodes (LEDs).     

Visible up-conversion and NIR luminescence studies of LiAl<Subscript>5</Subscript>O<Subscript>8</Subscript>:Er phosphor co-doped with Yb<Superscript>3+</Superscript> and Zn<Superscript>2+</Superscript>

The frequency up-conversion, an efficient laser emission and amplification in Er³⁺:LiAl₅O₈ phosphors co-doped with Yb³⁺ and Zn²⁺ phosphor powders in the 520–560, 640–680 nm regions and at ∼1.5 μm, respectively, have been reported. The emission corresponds to the ²H_11/2, ⁴S_3/2→⁴I_15/2, ⁴F_9/2→⁴I_15/2 and ⁴I_13/2→⁴I_15/2 transitions upon direct excitation into the intermediated ⁴I_11/2 level using ∼980 nm radiation from a CW laser. Possible mechanisms involved for the up-conversion processes based on the energy level matching scheme, the pump-power dependence and the dynamical behaviour have been discussed. The effect of the addition of Yb³⁺ and Zn²⁺ for the amplification in the 1.5 μm eye-safe telecommunication window has been elaborated and characterized in detail.