类镍等电子系列离子M1,M2,E2禁戒跃迁特性的理论研究

利用基于全相对论框架下的多组态Dirac-Fock理论方法发展起来的程序包GRASP92和新发展的处理辐射跃迁过程的程序REOS99，计算了类镍等电子系列离子(Z=45—95)的基组态3s²3p⁶3d¹⁰¹S₀以及低激发组态3s²3p⁶3d⁹4l,3s²3p⁵3d¹⁰4l和3s3p⁶3d¹⁰4l(l=s,p,d,f)的能级及其向基态的M1,M2,E2禁戒跃迁概率.通过分析高离化类镍离子在特定的原子序数范围内由于存在能级交叉而产生的强组态相互作用，解释了高离化类镍离子禁戒跃迁概率的反常变化现象，探讨了禁戒跃迁概率受强组态相互作用影响而变化的一般规律.     

Eu3+在M3La2(BO3)4(M=Ca,Sr,Ba)中的发光性质

本文报导了M3La2(BO3)4:Eu3+(M=Ca,Sr,Ba)磷光体的制备方法及晶体结构。三种磷光体均属正交晶系。研究了Eu3+离子的光谱特征与基质化合物的关系。发现在三种磷光体中,被Eu3+所取代的La3+离子均只有一种格位,且在此格位上不具备反演操作的对称性;Eu3+在Ca3La2(BO3)4:Eu3+中所处格位的局部对称性最低,属C1,C2和Cs中之一种,在M3La2(BO3)4:Eu3+(M=Sr,Ba)中Eu3+所处格位的局部对称性可能为C2v。     

Cr2MC(M=Al, Ga)的电子结构、弹性和热力学性质的第一性原理研究

本文使用第一性原理的GGA/RPBE方法研究了Cr₂MC(M=Al, Ga)的电子结构、弹性和热力学性质. 研究发现两个化合物的体积压缩性几乎相同, 并且证实了在0—50 GPa范围内c轴始终较a轴更难以压缩并且结构始终是稳定的. 通过对内坐标的研究发现了Cr₂AlC中Cr离子的内坐标始终大于Cr₂GaC中Cr离子的内坐标. 使用准谐德拜模型得到的体弹模量在0 GPa下随着温度的升高而减小, 而在300 GPa下则随着温度的升高而增大. 对德拜温度的研究发现Cr₂GaC的值小于Cr₂AlC的值, 而对热膨胀系数、Grüneisen参数、熵和热容的计算发现Cr₂GaC的值大于Cr₂AlC的值. 对电子结构的分析发现Cr₂GaC的s和p电子在费米能级处的值大于Cr₂AlC的s和p电子的值, 而其他离子的电子分布几乎一致.     

内掺过渡金属非典型富勒烯M@C22(M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni) 几何结构、电子结构、稳定性和磁性的密度泛函研究

采用密度泛函理论中广义梯度近似对非典型富勒烯C₂₂和过渡金属内掺衍生物M@C₂₂(M=Sc,Ti,V,Cr,Mn,Fe,Co和Ni)的几何结构和电子结构进行计算研究.发现非典型富勒烯C₂₂的基态结构是含有一个四碳环的单重态笼状结构.过渡金属原子的掺入明显提高了体系的稳定性. C-M键既有一定共价性又有一定离子性.磁性、能级图、轨道分布和态密度图分析表明: M原子的3d轨道和碳笼的C原子的原子轨道之间存在较强的轨道杂化. Ti, Cr, Fe和Ni内掺的结构出现磁性完全猝灭现象. Sc和碳笼间是弱反铁磁作用, V,Mn和Co与碳笼间是弱铁磁作用.     

MMgF_4：Eu（M＝Ca，Sr，Ba）体系中铕离子的发光中心及价态

合成了铕离子激活的ＭＭｇＦ４．磷光体，研究了Ｅｕ３＋离子的光谱特征与基质化合物的关系，存在三类发光中心，讨论了基质组成对铕离子价态的影响。     

Na5Eu(MO4)4(M=Mo,W)的B(λkq)强度参数和跃迁几率

本文应用Judd-Ofelt理论,从实验光谱数据得到了Na5Eu(MO4)4(M=Mo,W)的B(λkq)唯象参数.由这些B(λkq)线—线跃迁强度参数计算得到的5D0,1(ri)→7FJ(rf)的跃迁几率同实验光谱数据得到的跃迁几率较好地相吻合.本文对计算数据和实验结果之向存在的偏差作了讨论.     

GMPLS网络中基于优先级的M : N保护

给出了一个GMPLS网络中关于广义标签交换通道(G.LSPs)的具有严格优先级M : N保护的排队模型,并通过仿真验证了本模型的正确性.该模型可用于基于优先级的M : N保护设计,通过适当选择保护通道数,可以确保一定的可靠性要求,同时避免过度配置而造成资源浪费.     

异质富勒烯C19M(M=Cr,Mo,W)的结构和电子性质的计算研究

采用密度泛函理论(DFT)中的B3LYP方法, 在LANL2DZ基组水平上, 优化了C₁₉M(M=Cr,Mo,W)团簇的几何结构, 得出了它们的基态构型, 并研究了基态结构的物理化学性能.结果表明: 不同的M原子替换后, C₁₉M的动力学稳定性相差不大, 而热力学稳定性随着M原子序数的增加而逐渐升高; 通过对C₁₉M的前线轨道分析发现, M原子对各个轨道均有一定的贡献, M原子对各个轨道的贡献大致随着M原子序数的增加而增加, C₁₉M中金属原子M(M=Cr,Mo,W)上集中了大量的正电荷; C₁₉M的芳香性随着M原子序数的增加而减弱.     

GeO2-Bi2O3-MOx(MOx=WO3, BaO)玻璃近红外超宽带发光的研究

用高温熔融法制备了(99.5-χ) GeO₂-χBaO-0.5Bi₂O₃(χ=3, 6, 9mol%)与(99.5-φ)GeO₂-φWO₃-0.5Bi₂O₃(φ=3，6，9mol%)玻璃，测定了样品的发射光谱(800nmLD激发)、吸收光谱、荧光衰减和差热曲线.实验结果表明，在GeO₂-WO₃-Bi₂O₃系统玻璃中，随着WO₃含量的增加，在1260nm处的发光强度增强，荧光半高宽(FWHM)增宽，荧光寿命增长，而且玻璃的吸收边带发生明显的红移；在GeO₂-BaO-Bi₂O₃系统玻璃中，随着BaO含量的增加，玻璃在1290nm处发光强度增强，FWHM增宽，荧光寿命增长，吸收边带也有明显的红移.从吸收边带发生红移的情况，结合发射光谱和荧光衰减曲线特性，我们推断玻璃样品在近红外的宽带发光可能由Bi⁵⁺离子所引起.从荧光特性估算了玻璃的σ_p×τ和σ_p×Δλ值，这些玻璃均具有较小的σ_p×τ和较大的σ_p×Δλ特性，说明GeO₂-Bi₂O₃-MO_x(MO_x=WO₃, BaO) 系统玻璃是研制成近红外(O到S波段)超宽带光纤放大器的良好材料.     

129Xe30+与Au作用激发的Au M-X射线 与Xe L-X射线

探测了动能为1.0——7.0 MeV的¹²⁹Xe³⁰⁺ 入射Au表面产生的X射线谱. 实验结果表明, 入射离子动能较高时, 不仅激发出很强的Au的M-X射线, 还激发出了Xe的L-X射线, 且X射线产额与入射离子动能有强相关性. 分析了X射线产额与入射离子动能的关系.     

Influence of co‐dopant in the europium reduction in SrAl2O4 host

Xerogels of strontium chlorate and aluminium chlorate doped with europium (un‐co‐doped) and co‐doped with rare earth ions (Ln = Gd, Dy, Er and Y) were prepared using the proteic sol–gel route. Synchrotron radiation was used to investigate the effect of different co‐dopants on the Eu³⁺→ Eu²⁺ reduction process during the synthesis of the samples. Samples were excited at the Eu L_III‐edge and the XANES regions were analyzed. The results suggest that some of the Eu ions can be stabilized in the divalent state and that it is difficult to completely reduce Eu³⁺ to Eu²⁺ during thermal treatment. The mechanisms of the Eu reduction processes are explained by a proposed model based on the incorporation of charge‐compensation defects.     

Eu3+在硼酸盐玻璃中的发光以及Bi3+对Eu3+的敏化作用

本文研究了单掺和双掺(Eu3+,Bi3+,Fu3++Bi3+)约二十余种不同成份的硼酸盐玻璃,探讨了玻璃成份对Eu3+发光性质的影响和Bi3+对Eu3+的敏化作用.     

纳米级碱土金属钒酸盐发光材料[A3(VO4)2:Eu]发光性质的研究

采用Pechini型溶胶-凝胶法制备出系列纳米级铕掺杂的碱土金属钒酸盐.并采用电镜,红外光谱,室温荧光光谱对粉体的性质进行表征.结果表明所制备的粉体的粒径在20～50 nm之间,并且这些发光粉的性质与碱土金属离子的半径密切相关;由于Ca2 离子的半径与Eu3 的最接近,因而Eu3 更容易进入其晶格,表现出好的发光性质.     

Structure and luminescence of CsI:Eu columnar films

Europium doped columnar films of CsI are produced by vacuum condensation. Eu²⁺ ions in the CsI:Eu films lead to the formation of a narrow (0.18 eV), intense luminescence band with a maximum at 456 nm, which is excited by x-rays, as well as by photons of various energies. The spectral and kinetic characteristics of the emission depend on the amount of activator and on the conditions under which the film is prepared and stored. The nature of the luminescence centers is determined by structural formations that contain divalent europium ions.     

Luminescence of YAG doped with Eu,Yb, and Mn ions under VUV excitation

Hydrothermal synthesis has been successfully used to obtain fine-crystalline powders of yttrium aluminum garnet (YAG) doped with manganese ions and codoped with cerium and manganese ions. Using the method of high-temperature solid-state synthesis, ceramic specimens of YAG that contain europium and ytterbium ions have been obtained. In synthesized YAG:Eu and YAG:Yb ceramics, no luminescence that can be attributed to 5d-4f transitions in Eu²⁺ or Yb²⁺ ions has been detected, even though the scheme of energy levels of these ions constructed with respect to YAG energy bands indicates that there is a potential possibility of the occurrence of 5d-4f luminescence for Eu²⁺ ions in YAG. At room temperature, the luminescence spectrum of hydrothermally synthesized YAG doped with manganese ions consists of two broad bands with maxima at ～600 and ～750 nm and does not contain any narrow bands in the red or IR range. Therefore, the spectrum contradicts to the properties of the luminescence of Mn²⁺, Mn³⁺, or Mn⁴⁺ ions in YAG described in the literature, even though the obtained hydrothermal specimens can contain noticeable concentrations only of Mn³⁺ ions.     

Monoclinic centers of rare-earth <Emphasis Type="Italic">S</Emphasis> ions in yttrium orthoaluminate crystals

The ESR spectrum of Gd³⁺ and Eu²⁺ monoclinic centers, which substitute for yttrium ions in YAlO₃ crystals doped with europium and zirconium, has been investigated. Parameters of the fine structure of these centers are determined. The hyperfine-interaction parameters are determined for the centers with ¹⁵¹Eu isotope, and the hyperfine structure of the centers with ¹⁵³Eu isotope is discussed.     

The crystallinity and the photoluminescent properties of spray pyrolized ZnO phosphor containing Eu and Eu ions

A europium doped ZnO (ZnO:Eu) particle was directly synthesized by the spray pyrolysis method. The crystal structure of samples was designated by the europium ion and the synthesis temperature. We identified the coexistence of Eu²⁺ and Eu³⁺ ions in the as prepared ZnO, which was strongly influenced by the doping concentration and the synthesis temperature. With addition of a 0.5 mol% concentration of europium ions, only the Eu²⁺ ion existed in particles, while both Eu²⁺ and Eu³⁺ ions existed in sample using 1 mol% or higher concentration of europium ions. Changing the wavelength of the excitation source, we also found that both the blue and red luminescence can be obtained.     

Photoluminescence of colloidal YVO4:Eu/SiO2 core/shell nanocrystals

YVO₄:Eu, and YVO₄:Eu/SiO₂ nanocrystals (NCs) were prepared by hydrothermal method with citrate as capping ligands. Their morphologies, structures, components, and photoluminescence properties were investigated and presented in this paper. A remarkable fluorescence enhancement up to 2.17 times was observed in colloidal YVO₄:Eu/SiO₂ NCs, compared to that of colloidal YVO₄:Eu NCs. This is mainly attributed to the formation of the outer protecting layers of biocompatible SiO₂ shells; which shield the Eu³⁺ ions effectively from water and thus reduces the deleterious effects of water on the luminescence. Meanwhile, on the basis of laser selective excitation, two kinds of luminescent centers were confirmed in the NCs, namely, inner Eu³⁺ ions and surface Eu³⁺ ions. The surface modifications for YVO₄:Eu NCs effectively reduced the surface defects and accordingly enhanced the luminescence. The core/shell NCs exhibited long fluorescence lifetime and high photostability under ultraviolet radiation.