La2CaBl0O19：Ce3＋在VUV-Vis范围的发光性质研究

通过研究La2CaB10O19:Ce3 在VUV-Vis范围的光谱，发现Ce3 在La2CaBl0O19中共有两种格位．分别取代了十配位的La3 和八配位的Ca2 ．从而发射光谱中没有出现特征的双峰。而出现了峰值约位于307．330和356nm的3个发射峰．由于在低对称性晶体场中d轨道的分裂．激发光谱中位于194，224,243,260,274和318nm的峰是由两个格位的Ce3 的f-d跃迁引起的．Ce^3 占据两个格位．可以通过以Eu3 为荧光探针的发射光谱中出现的两个5Do-7Fo跃迁得到验证．峰值位于162nm的激发谱带是基质吸收带．与基质禁带宽度相对应．通过计算．不排除其中包含O2-→Ce3 的电荷迁移带的可能性．     

La2CaB10O19∶Ce3+在VUV-Vis范围的发光性质研究

通过研究La2CaB10O19∶Ce3+在VUV-Vis范围的光谱, 发现Ce3+在La2CaB10O19中共有两种格位, 分别取代了十配位的La3+和八配位的Ca2+, 从而发射光谱中没有出现特征的双峰, 而出现了峰值约位于307, 330和356 nm的3个发射峰.由于在低对称性晶体场中d轨道的分裂, 激发光谱中位于194, 224, 243, 260, 274和318 nm的峰是由两个格位的Ce3+的f-d跃迁引起的.Ce3+占据两个格位, 可以通过以Eu3+为荧光探针的发射光谱中出现的两个5D0-7F0跃迁得到验证.峰值位于162 nm的激发谱带是基质吸收带, 与基质禁带宽度相对应.通过计算, 不排除其中包含O2-→Ce3+的电荷迁移带的可能性.     

La2CaB10O19∶Eu3+的VUV-VIS范围光谱的研究

研究了La2CaB10O19∶Eu3+红色发光材料的高分辨发射光谱和UV-VUV激发光谱. 根据发射光谱和荧光寿命, 认为进入晶格的Eu3+占据了两种格位, 一种Eu3+占据了与O2-离子十配位的La3+的格位, 另一种Eu3+则占据了与O2-离子八配位的Ca2+的格位. 又从激发光谱的分析中, 得到Eu3+的电荷迁移带(CTB)是峰值位于244 nm的宽带, 而位于130～170 nm之间的成份复杂的宽带包括硼酸盐基质的吸收带和Eu3+的f-d跃迁的结论.     

Ce~(3+),Mn~(2+)共掺NaYF_4微米六棱柱的发光性能和能量传递研究

通过水热法合成了单分散的六方相NaYF_4:5%Ce~(3+),x%Mn~(2+)(摩尔分数,x=0,5,10,15)微米六棱柱。扫描电镜(SEM)分析表明,样品尺寸均匀,平均长度和平均高度约为2.02μm和700 nm。NaYF_4:5%Ce~(3+),x%Mn~(2+)发光性质的研究结果表明,在激发谱中,245 nm的激发峰来自于Ce~(3+)的4f→5d跃迁;332 nm的激发峰对应于Mn~(2+)的6A1(6S)→4E(4D)跃迁和自陷激子(STE)的激发。在发射谱中,302和422 nm的宽带发射峰分别对应Ce~(3+)的5d→4f跃迁和基质中自陷激子的发光;538和587 nm的宽带发射峰分别对应Mn~(2+)的~4A_1(~4G)→6A1(6S)跃迁和4T1(4G)→6A1(6S)跃迁。随着Mn~(2+)含量的增加,Ce~(3+)的发射强度逐渐减弱,而Mn~(2+)的538 nm(~4A_1(~4G)→6A1(6S))发射峰强度逐渐增强,这表明在NaYF_4基质中,存在Ce~(3+)和Mn~(2+)之间的能量传递。     

La_7O_6(BO_3)(PO_4)_2∶Eu~(3+)/Tb~(3+)荧光材料的制备及其光致发光性能

采用优化的高温固相方法制备了稀土离子Eu~(3+)和Tb~(3+)掺杂的La_7O_6(BO_3)(PO_4)_2系荧光材料,并对其物相行为、晶体结构、光致发光性能和热稳定性进行了详细研究。结果表明,La_7O_6(BO_3)(PO_4)_2∶Eu~(3+)材料在紫外光激发下能够发射出红光,发射光谱中最强发射峰位于616 nm处,为5D0→7F2特征能级跃迁,Eu~(3+)的最优掺杂浓度为0.08,对应的CIE坐标为(0.610 2,0.382 3);La_7O_6(BO_3)(PO_4)_2∶Tb~(3+)材料在紫外光激发下能够发射出绿光,发射光谱中最强发射峰位于544 nm处,对应Tb~(3+)的5D4→7F5能级跃迁,Tb~(3+)离子的最优掺杂浓度为0.15,对应的CIE坐标为(0.317 7,0.535 2)。此外,对2种材料的变温光谱分析发现Eu~(3+)和Tb~(3+)掺杂的La_7O_6(BO_3)(PO_4)_2荧光材料均具有良好的热稳定性。     

La2CaB10O19：Eu^3＋的VUV—VIS范围光谱的研究

研究了La2CaB10O19:Eu^3 红色发光材料的高分辨发射光谱和UV－VUV激发光谱，根据发射光谱和荧光寿命，认为进入晶格的Eu^3 占据了两种格位，一种Eu^3 占据了与O^2-离子十配位的La^3 的格位，另一种Eu^3 则占据了与O^2-离子八配位的Ca^2 的格位，又从激发光谱的分析中，得到Eu^3 的电荷迁移带（CTB）是峰值位于244mm的带，而位于130－170nm之间的成份复杂的宽带包括硼酸盐基质的吸收带和Eu^3 的f-d跃迁的结论。     

在La_2Na_2Sr_6(PO_4)_6Br_2基质中Tb~(3+)的发光及Ce~(3+)对Tb~(3+)的敏化

用高温固相反应法合成了发光材料、研究了Tb~(3+)在La_2Na_2Sr_6(PO_4)_6Br_2基质中的光致发光性质及Ce~(3+)对Tb~(3+)的敏化作用.在254nm紫外光激发下,Tb~(3+)的发光较弱,但Ce~(3+)对Tb~(3+)有强的敏化作用,其能量传递机埋是偶极-偶极相互作用引起的共振能量传递,计算了传递效率。     

La_(2.4)Mo_(1.6)O_8∶Yb~(3+),Er~(3+)材料的制备及其上转换发光性质

采用高温固相法制备了La_(2.4)Mo_(1.6)O_8∶Yb~(3+),Er~(3+)荧光粉。通过X射线衍射(XRD)和上转换发射光谱对样品进行了相结构和发光性质表征。XRD实验结果表明:合成的样品为面心立方萤石结构(Fm-3m)的La_(2.4)Mo_(1.6)O_8相。在980 nm红外光激发下,La_(2.4)Mo_(1.6)O_8∶Yb~(3+),Er~(3+)荧光粉发出分别来自Er~(3+)离子的~2H1_(1/2)→~4I_(15/2)、~4S_(3/2)→~4I_(15/2)跃迁的绿光(主峰为548和529 nm)和~4F_(9/2)→~4I_(15/2)跃迁的红光(主峰为670 nm)。进一步地,对样品中可能的上转换发光机制进行了讨论。     

Eu~(3+)在RE_2O_3·0.95P_2O_5·0.1SiO_2(RE=La,Gd)中的发光

研究了Eu~(3+)在RE_2O_3·0.95P_2O_5·0.1SiO_2(RE=La,Gd)基质中的发光。它们的激发光谱包括Eu~(3+)的CTS和f—f跃迁引起的吸收,于254nm附近有强的吸收。另外Gd基质试样在274nm处有一锐线吸收,是由Gd~(3+)的~8S→~6I跃迁产生的,表明Gd~(3+)可以把吸收的274nm波长的能量传递给Eu~(3+)。发射光谱只包括~5D_0→~7F_(0,1,2,3,4)跃迁的窄带谱。讨论了Eu~(3+)在La-Gd基质二元体系中的发光。随着Gd~(3+)含量的变化,可引起发射峰相对强度、CTS能量和发光亮度的连续变化。同时本文对Gd基质中Bi~(3+)通过Gd~(3+)的中间作用向Eu~(3+)传递能量进行了初步讨论。     

钡取代锶对Sr_3Al_(0.6)Si_(0.4)O_(4.4)F_(0.6):Ce~(3+)荧光粉的发光性能影响

采用高温固相法合成Ba取代Sr_3Al_(0.6)Si_(0.4)O_(4.4)F_(0.6):Ce~(3+)中Sr的氟氧铝硅酸锶钡(Sr_(3-x)Ba_xAl_(0.6)Si_(0.4)O_(4.4)F_(0.6):Ce~(3+))荧光粉。指出Ba/Sr固溶极限为x=0.9。由于Sr_3Al_(0.6)Si_(0.4)O_(4.4)F_(0.6):Ce~(3+)中Sr具有十配位Sr(1)和八配位的Sr(2),所以激活剂离子Ce~(3+)也具有两个不同的占位,通过Ce~(3+)的光谱结果,指出是由于Ba的掺入诱导Ce(1)~(3+)发光中心增加,减少了Ce(2)~(3+)发光中心,从而出现随着Ba/Sr比增加,粉样在400 nm激发下发光强度减小,而在460 nm激发下发光强度增强的现象。因此Sr_(3-x)Ba_xAl_(0.6)Si_(0.4)O_(4.4)F_(0.6):Ce~(3+)荧光粉是一款潜在的适合近蓝光激发的白光LED用荧光粉。     

OH(3) (-) and O(2)H(5) (-) double Rydberg anions: predictions and comparisons with NH(4) (-) and N(2)H(7) (-)

A low barrier in the reaction pathway between the double Rydberg isomer of OH(3) (-) and a hydride-water complex indicates that the former species is more difficult to isolate and characterize through anion photoelectron spectroscopy than the well known double Rydberg anion (DRA), tetrahedral NH(4) (-). Electron propagator calculations of vertical electron detachment energies (VEDEs) and isosurface plots of the electron localization function disclose that the transition state's electronic structure more closely resembles that of the DRA than that of the hydride-water complex. Possible stabilization of the OH(3) (-) DRA through hydrogen bonding or ion-dipole interactions is examined through calculations on O(2)H(5) (-) species. Three O(2)H(5) (-) minima with H(-)(H(2)O)(2), hydrogen-bridged, and DRA-molecule structures resemble previously discovered N(2)H(7) (-) species and have well separated VEDEs that may be observable in anion photoelectron spectra.     

Mixed ligand titanium(IV) complexes. Chlorobis(dithiocarbamato)bis(methylsalicylato)titanium(IV) andbis(dithiocarbamato)bis(methylsalicylato)titanium(IV)

Summary Dichlorobis(methylsalicylato)titanium(IV) reacts with potassium or amine salts of dialkyl or diaryl dithiocarbamates in 11 and 12 molar ratios in anhydrous benzene (room temperature) or in boiling CH₂Cl₂ to yield mixed ligand complexes: (AcOC₆H₄O)₂ Ti(S₂CNR₂)Cl (1) and (AcOC₆H₄O)₂ Ti(S₂CNR₂)₂ (2), R=Et, n-Pr, n-Bu, cyclo-C₄H₈ and cyclo-C₅H₁₀. These compounds are moisture sensitive and highly soluble in polar solvents. Molecular weight measurement in conjunction with i.r.,¹H and¹³C n.m.r. spectral studies suggest coordination number 7 and 8 around titanium(IV) in (1) and (2) respectively.     

Bis(trifluoroacetyl) peroxide, CF(3)C(O)OOC(O)CF(3)

Pure, highly explosive CF(3)C(O)OOC(O)CF(3) is prepared for the first time by low-temperature reaction between CF(3)C(O)Cl and Na(2)O(2). At room temperature CF(3)C(O)OOC(O)CF(3) is stable for days in the liquid or gaseous state. The melting point is -37.5 degrees C, and the boiling point is extrapolated to 44 degrees C from the vapor pressure curve log p = -1875/T + 8.92 (p/mbar, T/K). Above room temperature the first-order unimolecular decay into C(2)F(6) + CO(2) occurs with an activation energy of 129 kJ mol(-1). CF(3)C(O)OOC(O)CF(3) is a clean source for CF(3) radicals as demonstrated by matrix-isolation experiments. The pure compound is characterized by NMR, vibrational, and UV spectroscopy. The geometric structure is determined by gas electron diffraction and quantum chemical calculations (HF, B3PW91, B3LYP, and MP2 with 6-31G basis sets). The molecule possesses syn-syn conformation (both C=O bonds synperiplanar to the O-O bond) with O-O = 1.426(10) A and dihedral angle phi(C-O-O-C) = 86.5(32) degrees. The density functional calculations reproduce the experimental structure very well.