类镓等电子序列ZrX—RhXV离子的4s^24p—4s^24d,4s^24p—4s4p^2,4s^24 …

本文对类镓等电子序列ＧａＩ－ＸｅＸＸＩＶ离子４ｓ＾２４ｐ、４ｓ＾２４ｐ、４ｓ＾２４ｄ、４ｓ４ｐ＾２、４ｐ＾３和４ｓ＾２５ｓ组态组级结果和组态相互作用了理论分析，找出沿等电子序列的变化规律。     

KrVI离子能级和振子强度的理论计算

利用组态相互作用理论和参数外推法,计算了KrVI离子4s~24p—4s4p~2、4s~24p—4s~24d和4s4p~2—4p~3跃迁的能级、谱线波长和振子强度。与已有实验结果比较表明:波长的理论计算值与观测值在0.7A内很好符合,振子强度的理论计算值较大的跃迁均是实验中观测到的跃迁。     

RuXIV离子能级和振子强度的理论计算

利用组态相互作用理论和参数外推方法,计算RuXIV离子4s²4p,4s4p² 4s²4d和4p³组态的能级,以及4s²4p—4s4p²,4s²4p—4s²4d和4s4p²—4p³跃迁的谱线波长和振子强度。4s²4p和4s4p²组态的能级与已有实验 关键词：     

New energy levels and transitions for the 4s4p5p configuration in Kr VI

The spectrum of five-time ionized krypton, Kr VI, was recorded in the 240-2600 Å wavelength range, resulting in 61 new classified lines as transitions between levels of configurations 4p³, 4s²5p, 4s4p4d, 4s4p5s and 4s4p5p. All the 18 energy levels belonging to 4s4p5p configuration except one were determined. Eight new energy level values corresponding to configurations 4s4p4f and 4p24d, supported by 26 new classified lines were also determined and used in the interpretation of the observed 4s4p5p configuration. The experimental data were obtained from a capillary-discharge tube and theta pinch light sources. Multiconfiguration Hartree-Fock calculations with relativistic corrections and a least-squares fitted parametric calculation has been carried out.     

Rh XⅢ—Cd XVI离子4s24p3—4s4p4能级与跃迁的理论计算

用HFR（Hartree-Fock with relativistic corrections）方法对Rb V—Cd XVI离子4s²4p³和4s4p⁴组态能级结构做了全面系统的理论计算研究. 通过分析能级结构参数的HFR理论计算值与基于实验能级拟合得到的计算值之比值随着原子序数Z_c变化的规律,运用广义拟合外推方法预言了这些离子能级结构参数. 由此进一步计算了Rh XⅢ,Pd XIV,Ag XV和Cd XVI离子4s²4p³（⁴S_3/2,²P_1/2,3/2,²D_3/2,5/2）和4s4p⁴（⁴P_1/2,3/2,5/2,²P_1/2,3/2,²D_3/2,5/2,²S_1/2）组态能级以及电偶极跃迁波长与振子强度. 研究表明,对于4s²4p³组态,单组态近似可以得到较满意的结果;而对于4s4p⁴组态,只有在考虑了4s²4p²4d的组态相互作用效应时,计算结果的准确性才能明显得到提高. 同时,本文还运用全相对论grasp2K-DEV程序包计算了Rh XⅢ—Cd XVI离子组态能级. 对于Rh XⅢ离子4s²4p³（²P_1/2）,Pd XIV离子4s²4p³（⁴S_3/2,²P_1/2,3/2,²D_3/2,5/2）和4s4p⁴（²P_1/2,3/2,²D_3/2,5/2,²S_1/2）,能级均无实验值;对于Ag XV和Cd XVI离子,截至目前还没实验能级数据,没有实验能级值的所有数据均仅来自本文的计算数值. 本文计算结果与已有实验值吻合得很好.     

Kinetics in surface reconstructions on GaAs(001)

We have successfully controlled the surface structures of GaAs(001) by changing incident As-molecular species. Under As4 fluxes, the c(4 x 4) reconstruction with Ga-As dimers [c(4 x 4)alpha structure] is obtained, but the formation of three As-As dimer structures [c(4 x 4)beta structure] is kinetically limited. On the other hand, the structure change from the (2 x 4), through c(4 x 4)alpha, to c(4 x 4)beta phases is observed under As2 fluxes. We found that the c(4 x 4)alpha structure is energetically metastable and provides a kinetic pathway for the structure change between the (2 x 4) and c(4 x 4)beta phases under As2 fluxes.     

PdⅩⅣ-CdⅩⅥ离子4s24p3和4s4p4组态精细结构能级与跃迁的扩展分析

用多组态HXR理论方法对KrⅣ-CdⅩⅥ离子4s^24p^3和4s4p^4组态的精细结构能级进行了分析计算。在已有研究工作的基础上,通过对4s^24p^3和4s4p^4组态能级的实验观测值与HXR计算结果之差AE沿等电子序列变化规律的分析．找出了△E随有效核电荷数Zc变化的规律,预言并计算了PdⅩⅣ-CdⅩⅥ离子4s^24p^3和4s4p^4组态能级,大部分预言计算值与实验结果的偏差小于100cm^-2。由此还进一步计算了PdⅩⅣ-CdⅩⅥ离子4s^24p^3—4s4p^4跃迁的谱线波长、振子强度和跃迁概率。结果表明：除了4s^24p^3D5/2-4s4p^4^2D5/2跃迁的谱线波长(29．992nm)与实验值相差0．018nm外．对于其余5条谱线．预言值与实验值的偏差均不超过0．005nm。     

激光诱导铜等离子体中激发态4d′~4F_(9/2)的瞬态特性

利用时间分辨光谱技术,研究了激光诱导Cu等离子体中激发态4d′4F9/2的形成及其辐射跃迁的瞬态特性。结果表明:电子离子复合、粒子间碰撞、自蚀吸收等过程在等离子体不同演化时刻,对激发态4d′4F9/2原子的制备起着不同作用。粒子间碰撞作用剧烈时,激发态4d′4F9/2原子以相同几率向低能态4p′4Do7/2及4p′4Fo9/2跃迁转移能量;等离子体辐射约500 ns后,粒子间相互作用变弱,激发态4d′4F9/2原子主要通过辐射谱线CuⅠ359.91 nm转移能量。     

RbⅧ—NbⅪ离子n=4complex跃迁谱线、波长和振子强度

用HXR方法计算了类锌等电子序列RbⅧ-NbⅫ离子n=4complex组态能级，通过对各能级值沿等电子序列的变化规律分析，找出了ⅦE随Zc变化的一种新的拟合公式，运用此公式和我们自己设计的FOR-TRAN程序对上述组态各能级值进行了系统的拟合计算，给出了4s^2-4s4p,4s4p-4s4d跃迁谱线波长和相应的振子强度。     

Mn2+、Mn4+共掺杂Zn2GeO4电子结构和光学性质的第一性原理的研究

利用第一性原理的局域密度近似（LDA）方法, 对Zn2GeO4, Mn2+掺杂Zn2GeO4,Mn2+、Mn4+共掺杂Zn2GeO4的光电性质进行了理论研究。结果表明,Mn2+、Mn4+掺杂可以提高Zn2GeO4的载流子浓度,从而改善Zn2GeO4的导电性。Mn2+离子的掺杂导致Zn2GeO4对光的吸收由紫外区域扩展到可见光区域, Mn2+、Mn4+共掺杂促进Zn2GeO4晶体对可见光的吸收能力大幅增加,因此Mn2+、Mn4+共掺杂Zn2GeO4可以用于制备高效率的光催化剂和发光材料。     

光诱导雄黄矿物同质异象变化的显微成像拉曼散射研究

利用拉曼光谱研究了激光照射诱导雄黄的同质异象变化,这些结果证实了下面的反应：由于As—As键相对较弱,首先As—As键被破坏,有1个S原子加入到As—As键中,形成As—S—As键。此时由As₄S₄(Realgar类型)变化为As₄S₅相,而As₄S₅处于不稳定状态,As₄S₅相变化为 Pararealgar时有1个S原子从As—S—As键中释放出来。释放出来的S原子又加入到另外1个As₄S₄(Realgar)中,引起As₄S₄(Realgar)相变化为As₄S₅,As₄S₅进而分裂为1个S原子和As₄S₄(Pararealgar类型)。照射促进雄黄经由 As₄S₅ 分子被转换成副雄黄。     

若干钠锗酸盐晶体和熔体的温致结构变化及其锗配位数的拉曼光谱研究

本文测定了Na4GeO4、Na2GeO3、Na2Ge4O9和Na4Ge9O20等晶体从273K到1413K升温及熔体的拉曼光谱,结合分析金红石型GeO2的相关结构和光谱,研究了其微结构单元在升温过程中的变化、熔体中的形态和锗的氧配位数及其温致变化。Na4GeO4和Na2GeO3晶体结构单元为GeO4四面体,在升温过程及其熔体中锗维持四配位。Na2Ge4O9和Na4Ge9O20晶体结构单元为GeO4四面体和GeO6八面体共存,升温过程中,GeO6八面体将发生结构转变,在熔融状态全部转变为GeO4四面体,并产生与钠离子等摩尔分数的非桥氧,在熔体中锗的氧配位数为4。研究还表明,桥氧的对称弯曲振动模可以反映不同微结构单元间的连接,并且随着温致结构的变化而产生特征性的变化。     

1—(4—吡啶甲酰)—4—芳基氨基硫脲类和3—(4—吡啶基)—4—芳基—1,2,4—三唑啉—5—硫酮类化合物~(13)C—NMR谱研究

本文测定了新合成的,具有生理活性的1-(4-吡啶甲酰)-4 -苯基氨基硫脲,1-(4-吡啶甲酰)-4-对氯苯基氨基硫脲,1-(4 -吡啶甲酰)-4-对溴苯基氨基硫脲3-(4-吡啶基)-4-苯基-1,2,4,-三唑啉-5-硫酮,3-(4-吡啶基)-4-对氯苯基-1,2,4,-三唑啉-5-硫酮,3-(4-吡啶基)-4-对溴苯基-1,2,4-三唑啉-5-硫酮六个新化合物的~(13)C-NMR谱,并通过~(13)C-NMR谱中的宽带去偶,偏共振及APT技术,模型化合物对照,讯号强度对比及芳基取代基常数计算等方法,进行了上述化合物~(13)C-NMR谱峰的归属,并得到了甲酰肼基在吡啶环4位取代后对吡啶环各碳所产生的取代基效应.     

Ca4LaNbMo4O20:Pr3+荧光粉的发光性质

采用高温固相法成功制备出荧光粉Ca₄LaNbMo₄O₂₀:Pr³⁺,通过X射线衍射分析了样品的结构,其结构与CaMoO₄结构相似。在Ca₄LaNbMo₄O₂₀:Pr³⁺的激发光谱中出现了NbO₄^3-和MoO₄^2-的电荷迁移(CTS)吸收和Pr³⁺离子的4f→4f5d激发跃迁,以及Pr³⁺-金属离子的价间电荷迁移(IVCT)吸收;另外在420~520 nm处,还观测到属于Pr³⁺离子的典型f-f激发跃迁。发射光谱中,在452 nm激发下,主要出现绿光和红光两种发射,其峰值位于490 nm和607 nm处,分别是Pr³⁺的³P₀→³H₄和¹D₂→³H₄的跃迁作用;在紫外287 nm激发下出现NbO₄^3-和MoO₄^2-发射和Pr³⁺离子的4f5d→4f跃迁宽带,以及Pr³⁺离子的4f→4f发射峰。     

m-BiVO_4与t-BiVO_4的电子结构和光学性质的第一性原理研究

采用第一性原理的密度泛函理论赝势平面波方法,计算了单斜m-BiVO_4与四方t-BiVO_4的电子结构和光学性质.计算结果表明:m-BiVO_4为间接带隙半导体,禁带宽度为2.171 e V,t-BiVO_4为直接带隙半导体,禁带宽度为2.644 e V;m-BiVO_4与t-BiVO_4均可吸收紫外光及可见光,m-BiVO_4还可以吸收部分红外光.     

RhXⅥ-InXX离子n=4 Complex跃迁谱线和振子强度的计算

 对类锌等电子序列ZnI–SnXXI离子n=4Complex组态的能级结构和组态相互作用进行了理论分析。通过分析HXR方法理论计算值与实验值之差DE随Zc的变化关系，找出了用于最小二乘拟合计算的半经验拟合公式，用此公式预测了CdXIX–InXX离子n=4Complex中至今还没有实验值的部分能级。给出了4s²-4s4p, 4s4p-4s4d跃迁波长和相应的HXR方法计算的振子强度，同时也对预测能级值的可靠性作了说明。     

Effect of the final-state interaction on the initial core–hole lifetime: the case of the 4s-hole lifetime of Sn metal

The first theoretical study of the effect of the final-state interaction on the initial core–hole lifetime is presented. The 4s-hole lifetime width of Sn metal is calculated by an ab-initio atomic many-body theory (Green’s function method). When the final-state interaction in the 4p4d two-hole state, created by the 4s⁻¹−4p⁻¹4d⁻¹ f super Coster–Kronig (CK) transition of the initial 4s hole, is explicitly taken into account, the ab-initio atomic many-body calculation of the 4s-hole X-ray photoelectron spectroscopy (XPS) spectrum of Sn atom can provide excellent agreement with experiment in both the 4s-hole energy and the 4s-hole lifetime width. Otherwise, the many-body calculation underestimates considerably the 4s-hole lifetime width. The 4p4d two-hole state interacts strongly with the 4d triple-hole state by the 4p⁻¹4d⁻¹−4d⁻³ f super CK transition. The interaction affects greatly the initial 4s-hole lifetime width.     

Up-conversion luminescence research of Er（0.5）：ZBLAN material for volumetric display application when excited by 1520nm laser

The up-conversion luminescence of the ZBLAN fluoride glass Er(0.5):ZBLAN, when excited by a 1520 nm semiconductor laser, is studied in this paper. The absorption and common-fluorescence spectra are also measured in order to understand the up-conversion clearly. It is found that there are seven strong up-conversion luminescence lines (406.97^m, 410.42 nm), (521.97^m, 527.56 nm), (542.38^m, 549.27 nm), (654.27^m, 665.70 nm), 801.57^m nm, 819.46 nm, and 840.00 nm, which can be recognized as the fluorescence transitions of ({}^2G^4F^2H)_{9/2}→{}^4I_{15/2},{}^2H_{11/2}→ {}^4I_{15/2},{}^4S_{3/2}→{}^4I_{15/2},{}^4F_{9/2}→{}^4I_{15/2}, {}^4I_{9/2}→ {}^4I_{15/2}, ({}^2G^4F^2H)_{9/2}→{}^4I_{9/2}, and {}^4S_{3/2}→{}^4I_{13/2} respectively. Meanwhile, the small up-conversion fluorescence lines 379.20 nm, 453.10 nm and 490.60 nm are the transitions of {}^4G_{11/2}→{}^4I_{15/2},{}^4F_{5/2}→{}^4I_{15/2} and {}^4F_{7/2}→ {}^4I_{15/2} respectively. It is interesting that the slopes of log F－logP curves, the double-logarithmic variation of up-conversion luminescence intensity F with laser power P, are different from each other for these observed up-conversion luminescence, this being valuable for the volumetric display. Comprehensive discussions find that the {}^4G_{11/2}→{}^4I_{15/2}, (^2G^4F^2H)_{9/2}→{}^4I_{15/2}, (^2H_{11/2}→{}^4I_{15/2},{}^4S_{3/2}→{}^4I_{15/2},{}^4F_{9/2}→ {}^4I_{15/2}), and {}^4I_{9/2}→{}^4I_{15/2} up-conversion luminescences are five-photon, four-photon, three-photon, and two-photon up-conversion luminescences respectively. It is found also that the absorption from ground-state {}^4I_{15/2} level to {}^4I_{13/2} level is very large, which is beneficial to the sequential energy transfer up-conversion to occur.     

基质发光材料Na5Eu(MoO4)4和NaEu(MoO4)2的制备和发光

本文研究了化学计量的基质发光材料Na5Eu(MoO4)4和NaEu(MoO4)2.它们都属于四方晶系,空间群为I41/α .NaEu(Mo04)2属于白钨矿(scheelite)结构,一个晶胞中有2个分子式NaEu(MoO4)2(z=2);而Na5Eu(Mo4O)4属于类自钨矿(scheelite-like)结构,一个晶胞中有4个分子式Na5Eu(MoO4)4(z=4).X射线衍射确定的晶胞常数,对Na5Eu(MoO4)4,α=1.1439nm和c=1.1486nm(密度d计算=4.01g/cm3,z=4);对NaEu(MoO4)2,α=0.5236nm和c=1.1439nm(密度d计算=5.24g/cm3,z=2).由差热法和X射线衍射法确定了Na2MoO4-Eu2(MoO4)3的相图.Na5Eu(MoO4)4分解为NaEu(MoO4)2的温度是700℃.本文确定了制备纯 Na5Eu(MoO4)和NaEu(MoO4)2的方法,并研究了上述两种材料的激发光谱和发光光谱.确定了用X射线粉末衍射谱和发光光谱鉴别Na5Eu(MoO4)4和NaEu(MoO4)2的方法.在365nm紫外光激发下,Na5Eu(MoO4)4的发光比Na5Eu(WO4)4的强得多,在室温下,Na5Eu(MoO4)4,NaEu(MoO4)2和Na5Eu(WO4)4的相对发光积分亮度比为3.8:3.2:1.0.     

Studies on the Interactions of 2, 4-Dinitrophenol and 2, 4-Dichlorphenol with Trypsin

The interactions of 2, 4-dinitrophenol and 2, 4-dichlorphenol with trypsin were investigated by fluorescence, synchronous fluorescence, and three-dimensional fluorescence spectra techniques under physiological pH 7.40. The 2, 4-dinitrophenol and 2, 4-dichlorphenol effectively quenched the intrinsic fluorescence of trypsin via static quenching. The process of binding 2, 4-dinitrophenol and 2, 4-dichlorphenol with trypsin was a spontaneous molecular interaction procedure. The electrostatic repulsion does favor the interaction between 2, 4-DNP and trypsin. However, the interaction of 2, 4-DCP and trypsin can be explained on the basis of hydrogen bonding and van der Waals. The results of synchronous fluorescence spectroscopy and three-dimensional fluorescence spectra indicated that the structure of these trytophan and tyrosine residues environments were altered by 2, 4-DNP and 2, 4-DCP.