U原子的组态,相互作用

本文用MCDF方法对U原子(5f~36d7s~2 5f~36d~27s)和(5f~26d~27s~2 5f~47s~2)的组态相互作用分别进行了研究。结果表明(5f~36d7s~2 5f~36d~27s)的组态相互作用比较强,而(5f~26d~27s~2 5f~47s~2的组态相互作用比较弱。     

Eu原子4f~76p_(3/2)6d自电离过程的动力学特性

采用孤立实激发技术(isolated-core excitation, ICE)及速度影像技术(velocity-map imaging,VMI),研究了Eu原子4f~76p_(3/2)6d自电离过程的动力学特性.孤立实激发技术用于将Eu原子从基态4f~76s~(2 8)S_(7/2)经中间态4f~76s6p激发到4f~76s6d里德堡态,然后将其进一步激发至4f~76p_(3/2)6d自电离态;速度影像技术用于探测其自电离过程的动力学特性,从而获得自电离衰变的分支比(branch ratio, BR)和弹射电子的角分布(angular distribution, AD).自电离衰变的分支比代表离子的能量分布,从中获得VMI影像的径向信息;而通过各向异性参数描述的弹射电子的角分布揭示了VMI影像的角向信息.此外,讨论了自电离衰变分支比和弹射电子角分布在整个自电离共振能域内的变化情况.基于4f~76s~+和4f~75d~+两个离子态的分支比,讨论了实现Eu离子粒子数反转的可能性.     

Yb原子里德伯态及价态的场电离阈

用偏振激光两步激发得到Yb原子不同|m|值的里德伯态和4f~(13)5d6s6p价态,采用脉冲场电离方法测定了6sns~1S_0(n=21—28),m=0和6snd~1D_2(n=20—27),|m|=0,1各里德伯态及4f~(13)5d6s6p价态的电离阈值。引入stark有效量子数n_s对电离阈值作了计算。对实验和计算结果作了对比分析。讨论了场电离过程中价态与里德伯态之间的相互作用及其对电离阈值的影响。 关键词：     

稀土元素Yb的高激发态结构Ⅱ偶宇称J=2能谱的MQDT分析

本文根据三阈五通道模型,对Yb偶宇称J=2能谱进行了MQDT分析,获得了修正的MQDT基本参量,并由此计算了6snd~(1,3)D_2(n=8-155)及6p~(21)D_2,4f~(13)5d6s6pA和4f~(13)5d6s6pB等共300个能位。结果十分合理地再现了现有实验观测值;对150个新能位的预言值迄今尚无类似文献报道先例。本文还计算了通道混合系数并对通道相互作用作了讨论。本文结果表明,本征量子亏损随激发能量的变化具有比通常采用的线性关系更为复杂的特征。     

Eu原子4f~76p_(1/2)ns自电离过程的动力学特性

采用孤立实激发与速度影像技术相结合的方法,研究了Eu原子4f~76p_(1/2)ns(n=7,9)自电离过程的动力学特性,包括弹射电子的角分布和向各离子态衰变的分支比.首先,采用孤立实激发技术将Eu原子分步从基态4f~76s~2经中间态4f~76s6p激发至4f~76sns Rydberg态,并通过第三步跃迁4f~76s~+→4f~76p_(1/2)~+。将其激发至4f~76p_(1/2)ns自电离态.其次,运用速度影像技术对上述自电离过程进行探测,并通过一系列数学变换计算出该过程的弹射电子的能量分布和角向分布本文不仅分析和比较了各个态自电离衰变的分支比和各向异性参数随光子能量的变化规律,还深入讨论了它们与自电离光谱之间的对应关系.最后,依据自电离衰变的分支比,探讨了实现Eu离子粒子数反转的可能性,为实现自电离激光器提供了有价值的信息     

稀土元素Yb的高激发态结构 I.偶宇称J=0能谱的MQDT分析

本文根据多通道量子亏损理论(MQDT),讨论了计算原子高激发态能谱的一般程式;使用我们新近建立的MQDT程序库,获得了Yb偶宇称J=~0MQDT基本参量,并对6sns~1S_0(n=7-252)及干扰态6P~(23)P_0、6P~(21)S_0、4f~(13)5d6s6pA和4f~(13)5d6s6pB等共250个能位进行了计算。结果不仅十分合理地再现了相应能域内全部实验观测结果,同时还对190个能位作了理论预言,其中l72个新预言能位迄今尚无类似文献报道先例。由于我们考虑了本征量子亏损对激发能量的高次依赖关系,对较低激发态能位的计算结果较Aymar等人的相应结果有了显著改善。     

Eu原子4f~76p_(3/2)ns自电离态的光谱的研究(英文)

采用孤立实激发技术,对铕原子4f~76p_(3/2)ns(n=7,8)自电离态的光谱进行了系统的研究,同时是首次在不同激光偏振组合下进行的研究。首先,用前两束激光分步将铕原子从基态4f~76s~2经中间4f~76s6p态激发至4f~76sns里德堡态,然后再用第三束激光通过离子实4f~76s~+→4f~76p~+_(3/2)的跃迁将其进一步激发至4f~76p_(3/2)7s自电离态或4f~76p_(3/2)8s自电离态。对铕原子4f~76p_(3/2)ns(n=7,8)自电离态复杂的光谱分别给出了详细的解释,从中我们可以获得一些重要的光谱信息,比如自电峰的能级位置和线宽等,同时还可以观察到收敛于不同离子限的自电离系列之间的组态相互作用。最后,通过比较不同激光偏振组合下的自电离光谱,确定了一些自电离态的总角动量的值。     

Eu~(2+)/Eu~(3+)掺杂的微晶玻璃发光特性研究

通过高温熔融法和热处理成功制备了白光发光的Eu~(2+)/Eu~(3+)掺杂SiO_2-Al_2O_3-ZnO-K_2CO_3微晶玻璃。测试了微晶玻璃的X射线衍射谱(XRD)、激发光谱和荧光光谱。研究发现,X射线衍射谱表明了玻璃基质中存在β-Zn_2SiO_4纳米晶粒,根据XRD结果和Scherrer公式计算得到β-Zn_2SiO_4晶粒大小约为35 nm。在紫外光激发下,观察到强烈的宽带蓝光(400～460 nm)和红光(574,587,611,650和700nm)发光,分别对应Eu~(2+)的4f~65d→4f~7能级跃迁以及Eu~(3+)的~5D_0→~7F_J(J=0,1,2,3,4)能级跃迁,与未热处理玻璃样品相比较,微晶玻璃的发光强度大大增强。研究结果表明,Eu~(2+)/Eu~(3+)掺杂的SiO_2Al_2O_3-ZnO-K_2CO_3晶玻璃是一种白光LED潜在的基质材料。     

铥原子收敛于4f~(13)(~2F~?_(7/2))6s(7/2,1/2)~?_4和4f~(13)(~2F~?7/2)6s(7/2,1/2)~?_3偶宇称里德伯系列能级的电子关联效应

本文在多通道量子亏损理论框架下,利用相对论多通道理论,计算了铥原子收敛于4f~(13)(~2F?_(7/2))6s(7/2,1/2)?_4和4f~(13)(~2F?7/2)6s(7/2,1/2)?_3的三个偶宇称里德伯系列.通过将计算结果与美国国家标准与技术研究院数据进行比较,展示了两种类型的电子关联效应:1)里德伯系列之间的相互作用,导致里德伯系列的能级出现整体偏移; 2)一个孤立的干扰态镶嵌在一个里德伯系列中,破坏了该里德伯系列能级的规则性.     

利用类铜离子谱线诊断银等离子体电子密度

测量了激光加热块状银靶产生的等离子体XUV光谱.计算了T_e分别为65eV,86eV和130eV时,AgXIX4s-4P,4P-4d,4d-4f7条谱线在不同电子密度时的强度.根据AgXIX4d~2D_(s/2~-)4f~2F_(r/2)和4P~2P_(3/2)-4d~2D_(s/2)两条谱线的强度比,推导了激光银等离子体电子密度.当入射激光功率密度W为6×10~(12)W/cm~2时,银等离子体电子密度N_e=1×10~(20)/cm~3. 关键词：     

Spectral properties of rare-earth ions in nanocrystalline YAG:Re (Re=Ce, Pr, Tb)

Bulk and nanoscale powders of YAG:Re (Re=Ce, Pr, Tb) were synthesized by solid-state and sol-gel method. The changes of spectra and energy level were studied. Compared with the bulk YAG:Re (Re=Ce, Pr, Tb) crystals, the lattice parameter of YAG:Re (Re=Ce, Pr, Tb) nanocrystals decreases. It is also found that the excitation peaks of 5d energy levels shift in nanocrystals. The physical reason for spectral and energy level changes is a comprehensive result from the shift of energy centroid of the 5d orbit, the Coulomb interaction between 4f and 5d electrons and the crystal field splitting of the 5d energy level.     

利用光电离技术研究奇宇称的Sm原子光谱

采用一台频率可扫描的染料激光器将Sm原子从4f66s2 7FJ(J=1,2)态分别激发到具有不同电子组态的若干原子态上,然后利用光电离技术对处于上述状态的Sm原子进行高灵敏探测.通过波长固定在355nm的紫外激光器,我们对一系列具有4f66s6p或者4f55d6s2电子组态的原子状态进行了精密的光谱测量.本实验研究不但确定了这些态的能级位置,还给出了它们的相对光谱强度.通过理论方法对光谱数据详细的分析,我们不但确认了文献中Sm原子的部分奇字称能级的位置和光谱标识,还同时给出了许多新的跃迁及其光谱特性.     

Influence of acceptor and donor adsorbates (CO,K, NH3) on Pt surface core-level shifts

4f core-level shifts have been measured for clean surfaces of Pt(111), Pt(331), and Pt(557). Surface peaks due to terrace sites are shifted toward lower binding energy (0.32 ± 0.05 eV) from the bulk peak, whereas peaks from step atoms are shifted by 0.58 ± 0.05 eV also to lower binding energy. The intensity ratios for the two sites differ considerably between the stepped Pt surfaces. Chemisorption of carbon monoxide on the Pt(331) surface is preferential to step sites, with a Pt 4f binding energy shift of ～ 1.29 eV toward higher binding energy. Chemisorption of potassium and ammonia also produces Pt 4f surface shifts which are at higher binding energy than the bulk peak. These experiments do not support the concept of electron donation by these adsorbates into metal d orbitals. The results are discussed in view of, and supported by, tight-binding LCAOMO calculations of potassium and ammonia interacting with a Pt(111) thin film.     

Reappearance of fine structure as a probe of lifetime broadening mechanisms in the 4f(N) --> 4f(N-1)5d excitation spectra of Tb3+, Er3+, and Tm3+ in CaF2 and LiYF4

High-energy transitions in the 4f(N) -->4f(N-1)5d excitation spectra of lanthanide ions in host crystals are usually broadened due to the short excited-state lifetimes, whereas low-energy transitions, with longer excited-state lifetimes, may show fine structure. We report the surprising observation that for some materials fine structure is observed not only for the low-energy excitation bands but also for some high-energy transitions. The excited states that display fine structure are those for which the 5d electron is in the lowest crystal-field level but the 4f(N-1) core is in a highly excited state, indicating that the broadening depends only on the energy of the 5d electron and not on the total energy of the 4f(N-1)5d excited state.     

掺杂三价铽离子的碱土金属钨酸盐的光谱特性研究

本文合成了一系列掺杂三价铽离子的碱土金属钨酸盐,测定了晶体的X射线粉末衍射数据及发射光谱和激发光谱.所合成的化合物均属四方晶系,I41/a空间群,晶胞多数随金属离子半径的增大而增大.研究了在这些晶体中三价铽离子5D3→7Fi和5D4→7Fi跃迁发射的激发态及其能量传递机理和浓度猝灭机制.讨论了发射光谱和激发光谱与铽离子浓度、金属离子半径及铽离子在晶体中的溶解度的关系.     

铜到钼的类钠离子能级结构及软X射线光谱理论计算

本文采用Hartree-Fock自洽场方法,从理论上计算了铜到钼的类钠离子1s~22s~22p~6nl(n=3～6,l=O～5)各能级能量。给出了有可能实现软X射线激光的跃迁(5g—4f,5f—4d,6g—4f,6f—4d)的光谱性质:跃迁波长、振子强度,并和实验值进行了比较,跃迁波长的相对误差不超过千分之二。从计算结果可知,Se的6f—4d跃迁,Br的6g—4f跃迁,Zr的5f—4l跃迁,Nb的5g—4f跃迁都已进入水窗波段。     

Tb3+掺杂Y2O3纳米晶体中Tb3+离子4f5d跃迁及能量传递的研究

采用燃烧法制备了不同Tb3 掺杂浓度和不同粒径的Y2O3:Tb纳米晶体粉末样品,并通过高温退火获得了相应Tb3 掺杂浓度的体材料样品。测量了纳米和体材料样品的发射光谱、激发光谱、X射线衍射谱和荧光衰减曲线,并拍摄了不同粒径样品的透射电子显微镜(TEM)照片。研究纳米Y2O3∶Tb晶体粉末中Tb3 离子的4f5d跃迁发现,由于在近表面的低结晶度环境和颗粒内部的高结晶度环境中Tb3 离子4f5d跃迁对应的激发峰位置不同,不同粒径样品中处于这两种环境的Tb3 离子比例也不同,激发谱的谱线形状存在较大差别,还对Tb3 离子的能量传递进行了研究,发现Y2O3∶Tb晶体粉末中Tb3 的(5D3,7F6)→(5D4,7F0)能量传递类型为受纳米限域效应影响很大的电偶极电偶极相互作用;引起5D4→7F5(543nm)发光浓度猝灭的是不同Tb3 离子5D4能级之间交换相互类型的能量传递,此类型的能量传递受纳米限域效应影响较小。     

Interplay of spin-allowed and spin-forbidden 5d–4f luminescence from rare earth ions

The conditions for co-existence of emissions from spin-allowed and spin-forbidden 5d–4f transitions in rare earth ions and for thermal quenching of these emissions have been analyzed by taking Tm³⁺ 5d–4f luminescence in LiYF₄:Tm³⁺ and Lu³⁺ 5d–4f luminescence in LuF₃ as examples. It is shown that temperature behavior of 5d–4f luminescence agrees with the common trends in decreasing energy splitting between the lowest high-spin and low-spin 5d levels as well as decreasing energy gap between the lowest 5d level and the bottom of the conduction band of the host crystal towards heavier rare earth ions (from Er³⁺ to Lu³⁺).     

Dissociative multiple photoionization of Br2, IBr,and I2 in the VUV and X-ray regions: a comparative study of the inner-shell processes involving Br(3d,3p,3s) and I(4d,4p,4s,3d,3p)

Dissociative multiple photoionization of the bromine, the iodine monobromide, and the iodine molecules in the Br(3d,3p,3s) and I(4d,4p,4s,3d,3p) inner-shell regions has been studied by using time-of-flight (TOF) mass spectrometry coupled to synchrotron radiation in the ranges of 90∼978 eV for Br₂, 60∼133 eV for IBr, and 86∼998 eV for I₂. Total photoion and photoion–photoion coincidence (PIPICO) yields have been recorded as functions of the photon energy. Here, giant shape resonances have been observed beyond the thresholds of the inner-shells owing to the Br(3d¹⁰)→Br(3d⁹ϵf), I(4d¹⁰)→I(4d⁹ϵf), and I(3d¹⁰)→I(3d⁹ϵf) transitions. The dissociation processes of the multiply charged parent ions have also been evaluated from variations of photoelectron–photoion coincidence (PEPICO) and PIPICO spectra with the photon energy. From each Br(3p_3/2) (189.9 eV) and I(4p_3/2) threshold (129.9 eV), quintuple ionization of the molecules begins to play important roles in the photoionization, subsequently yielding ion pairs of X³⁺–X²⁺ (X=Br, I). From the I(3d_5/2) threshold (627.3 eV), loss of six electrons from iodine molecule additionally begins to play a minor role in the multiple photoionization, giving rise to the formation of ion pairs of either I³⁺–I³⁺ or I⁴⁺–I²⁺. A direct comparison of the strengths and the ranges of the I(4d) and Br(3d) giant resonances was successfully made from dissociative photoionization of IBr. Over the entire energy range examined, 60<E<133 eV, biased charge spread relevant to the specific core-hole states of IBr is observed, presumably reflecting the fact that charge localizes mostly in the excited atoms, which can be accounted for mainly by a two step decay via a fast dissociation followed by autoionization upon the VUV absorption.