Microscopic Analysis of 5d States Splitting and Charge Transfer Energies Dependence on Interionic Distance in Alkaline Earth Fluorides Doped with Light Trivalent Lanthanides

A first principles fully relativistic analysis (K. Ogasawara et al., Phys. Rev. B 2001, 64, 115413) of the dependence of 5d orbitals splitting (10Dq) and charge transfer (CT) energies on interionic distance has been performed for light lanthanides (Ce³⁺, Pr³⁺, Nd³⁺) in CaF₂, SrF₂, BaF₂ crystals. The salient feature of the method is that four‐component molecular orbitals (MO) composed of atomic wave functions are used as the basis set. Without any fitting parameter, the power dependencies for 10Dq and linear dependencies for the CT energies on the distance between rare‐earth (RE) ions and ligands were obtained. A comparison with experimental values is discussed.     

Mn掺杂的碱土金属硫化物红外光激励发光及光存储性能的比较

采用硫化助熔剂法制备了SrS：Eu,Mn和CaS：Eu,Mn荧光粉。与CaS相比,SrS基质材料的光激励发光峰位于610 nm,比前者更接近视觉敏感区。比较了不同基质材料的存储光和量,SrS基质材料存储能力强于CaS。同时Mn2+掺杂增大了碱土金属硫化物被存储的光子数量,有利于提高材料的存储性能。     

Luminescence of Molecules with Internal Charge Transfer upon Longwave Excitation

We have studied the spectral properties of luminescence of laurdan molecules in glycerin upon excitation at the red edge of the absorption band at different temperatures. The most significant red-wave shift of the spectra (10 nm) for the longwave band of dual fluorescence is observed depending on the excitation wavelength at a low temperature of 260 K when a solvent forms a fairly rigid matrix. At the same time, at increased temperatures of up to 370 K a small bathochromic shift and a change in the shape of the luminescence bands are also recorded reliably. Changes in the excitation spectra were observed when luminescence was recorded in the bands of the LE- and CT states. The difference spectrum responsible for the additional absorption that does not make a contribution to the longwave luminescence component has been isolated. The decay kinetics of both luminescence components have been measured and their expansions in decay constants have been analyzed. The experimental dependences obtained point to the complex mechanism of inhomogeneous broadening of spectra.     

稀土氟化物Y0.97Er0.03F3纳米材料的制备及上转换发光

通过燃烧法和控温热反应法制备了稀土氟化物纳米材料，利用XRD和TEM对样品进行了分析和表征。测量了发射波长为980nm激光二极管激发下所得纳米材料的上转换发光性质。     

共轭低聚物中光生分子间电荷转移态的第一性原理研究

We perform density functional theory calculations to investigate the polaron pair (charge transfer state) photo-generation in donor-acceptor oligomer methyl-capped (4,7-benzo[2,1,3]thiadiazole-2,6-(4,4-bis (2-ethylhexyl)-4H-cyclopenta[1,2-b;3,4-b'']dithiophene-4,7-benzo[2,1,3]thiadiazole)(CPDTBT).Results show that effective photo-generation of charge transfer state can happen in CPDTBT dimer when the group 4,7-benzo[2,1,3]thiadiazole (BT) in one monomer deviates against the conjugated plane (onset torsion angle is about 20°).The lower excitation energy (530 nm) can only generate the intramolecular excitonic state,while the higher excitation energy (370 nm) can generate the intermolecular charge transfer state,in good agreement with the experiment.Moreover,the mechanism of charge separation in CPDTBT oligomers is discussed.     

稀土氟化物纳/微米材料的水热合成、形成机理和发光性质

研究了稀土氟化物纳/微米材料的设计合成、形貌控制、形成机制以及发光性质.发展了一种简单、整体、没有模板、环境友好的水热方法合成系列稀土氟化物,即用有机添加剂柠檬酸钠(Na3C6H5O7·2H2O)作为配位剂和形貌控制剂,通过改变氟源(NaF,NH4F或NaBF4)和最初溶液的pH值,得到了具有不同成分、晶体结构、尺寸和...     

Yb3+和Er3+共掺ZnF2-AlF3-PbF2-LiF 多晶和玻璃的光谱性质

研究了978nmLD激发下Yb^3 ,Er^3 共掺新的氟化物基质30ZnF2-25AlF3-30PbF2-15LiF多晶和玻璃中的上转换发光性质，分析了上转换发光的途径，重点讨论了多晶样品中红色上转发光增强的过程和原因。最后解释了Er^3 和Yb^3 共掺杂的氟氧化物玻璃陶瓷中奇特的发光现象。     

Visualization of Metal-to-Ligand and Ligand-to-Ligand Charge Transfer in Metal-Ligand Complexes

利用三种方法可视化化了Ru(II) ammine的金属到配体的电荷转移. 首先原子分辨的态密度显示HOMO上的密度主要在Ru上,LUMO 上的态密度在ammine上,这说明Ru上激发的电子会转移到ammine配体上. 第二,电荷差异密度揭示了所有的空穴都在Ru上,所有的电子都在ammine上. 第三,跃迁密度矩阵揭示了Ru和ammine上的电子空穴对的相关性. 这三种方法也用来研究Os(bpy)₂(p0p)Cl的金属到配体的电荷转移和Alq3配体到配体的电荷转移.     

荷移荧光光谱法测定加替沙星

研究了加替沙星(GFLX) 与电子受体四氯对苯醌(TCBQ)之间的荷移反应,建立了测定加替沙星的新方法。实验结果表明,在甲醇-水介质中于45 ℃水浴恒温20 min,GFLX与TCBQ可形成稳定的1∶1电荷转移络合物,其荧光发射强度较GFLX本身有显著的增强。在0.19～5.6 mg·L-1 浓度范围内,荧光强度与GFLX浓度呈良好的线性关系,检出限为0.005 6 mg·L-1。用于药物制剂中GFLX的含量测定,其回收率为101.1%～103.9%;标准偏差为1.0%～1.9%。同时建立了测定尿样中GFLX的荷移同步荧光光谱法,GFLX浓度在0.023～3.4 mg·L-1范围内与荧光强度呈良好的线性关系,检出限为0.003 4 mg·L-1。用本方法测定尿液中的GFLX,结果与文献值基本一致,回收率为93.9%～101.0%;标准偏差为1.0 %～1.7%。     

荷移分光光度法测定罗红霉素

本文研究确定了罗红霉素与甲酚红的荷移反应条件。在乙醇 丙酮介质中 ,罗红霉素与甲酚红在35℃的温度时发生荷移反应 ,产物的最大吸收波长为 456nm ,表观摩尔吸光系数为 1 0 5× 1 0 4L·mol- 1 ·cm- 1 ,罗红霉素的浓度在 0～ 80mg·L- 1 范围内与吸光度呈线性关系 ,相对标准偏差为 0 87% (n=6) ,回收率在 98%以上。测定了荷移络合物的组成比为 1∶1 ,探讨了反应机理 ,其中罗红素作为电子给予体、甲酚红作为电子接受体发生了电荷转移反应。     

两种新型电荷转移盐的合成和光谱研究

合成了两种新的有机盐[NO₂BzPy]Cl(1)和[NO₂BzPyNH₂]Cl(2),(1)[或(2)]与K[TCNQ]₂进一步反应生成[NO₂BzPy] [TCNQ]₂ (3)和[NO₂BzPyNH₂] [TCNQ]₂(4)。光谱数据表明：TCNQ盐中存在TCNQ0和TCNQ-,并形成了一维TCNQ分子柱,且TCNQ₀和TCNQ-之间存在相互作用,部分电荷从[TCNQ]-₂向阳离子([NO₂BzPy]+和[NO₂BzPyNH₂]+)转移。     

Near infrared and charge transfer luminescence of Yb-doped LaPO4 at room temperature

The Yb³⁺-doped LaPO₄ was prepared by hydrothermal reaction under fine acidity control and identified by X-ray diffraction and FT-IR spectroscopy. The obtained powders crystallize in the monoclinic phase of LaPO₄. The spectroscopic study at room temperature (RT) of the Yb³⁺-doped LaPO₄ powder was investigated. Thus a wide band, characteristic of the fundamental ²F_5/2↔²F_7/2 transition in near infrared (NIR) range, has been located for La_(1−x)Yb_xPO₄ (x = 5, 10%). Four Stark levels of the ground ²F_7/2 state are located on the emission spectra between 976 nm and 1030 nm, after excitation at 925 nm. Low re-absorption of the 0-phonon transition was registered. Charge transfer band (CTB) luminescence of Yb³⁺, which is not observed in LaPO₄ in later works, was appeared under 266 nm excitation. In the UV–Visible spectra, double band typical for the CTB luminescence of Yb³⁺ are observed. The decay time dependence as a function of the concentration is also reported and compared to other works. The room temperature radiative lifetimes of the IR emission and charge transfer band luminescence are compatible with potential applications of this phosphor respectively as solid-state lasers and scintillators.     

Pr,Yb:ZBLAN上转换发光过程中的能量传递

详细地研究了Ｐｒ３＋，Ｙｂ３＋ＺＢＬＡＮ玻璃中Ｐｒ３＋和Ｙｂ３＋离子之间的能量传递过程、及能量传递对上转换发光的影响。实验结果表明，在９６０ｎｍ激光泵浦下Ｙｂ３＋通过Ｙｂ３＋—Ｐｒ３＋之间的交叉弛豫向Ｐｒ３＋传递能量。具体的能量传递形式有三种。Ｙｂ３＋作为敏化剂可提高Ｐｒ３＋的上转换发光强度。从Ｐｒ３＋向Ｙｂ３＋的反向能量传递过程也是存在的，具体的过程和Ｐｒ３＋向Ｙｂ３＋传递的相反。Ｐｒ３＋—Ｙｂ３＋的能量传递导致Ｐｒ３＋发光的淬灭，使Ｐｒ３＋上转换发光随着Ｙｂ３＋浓度增加出现饱和。和３Ｐ０能级相比较，Ｙｂ３＋对Ｐｒ３＋离子的１Ｄ２能级发光的淬灭作用更强     

荷移分光光度法测定醋酸氯己定

通过醋酸氯己定与红紫素的荷移反应来测定制剂中醋酸氯己定的含量,是利用分光光度法进行测定的。反应在乙醇-丙酮介质中进行,反应物的最大吸收波长为545 mn,表观摩尔吸光系数为1.54×10~4 L·mol-1·cm-1,相对标准偏差为0.89％(n=6),药物浓度在0-45 mg·L-1范围内呈线性关系;此方法简便易行,条件易于控制,灵敏度高,对样品的测定结果令人满意。     

甲磺酸培氟沙星荷移反应及荧光光谱性质研究

研究了甲磺酸培氟沙星与电子受体四氯对苯醌之间的荷移反应 ,实验表明 ,在甲醇体系中 ,甲磺酸培氟沙星与四氯对苯醌在光的作用下可形成稳定的荷移络合物 ,其荧光发射强度较甲磺酸培氟沙星显著增强 ,且最大激发波长和发射波长向长波方向分别位移 80和 6 0nm。在 0 0 5～ 10 μmol·L-1浓度范围内 ,甲磺酸培氟沙星荧光强度与浓度呈良好线性关系 ,其检出限为 0 0 0 4 μmol·L-1。该方法用于甲磺酸培氟沙星胶囊中甲磺酸培氟沙星含量的测定 ,结果与紫外 可见光度法一致。     

克霉唑与茜素红的荷移反应研究

本文用分光光度法研究并确定了克霉唑与茜素红的荷移反应条件。在丙酮 水介质中形成 1∶1配合物 ,其λmax=5 2 5nm ,克霉唑浓度在 0～ 10 0 μg·mL-1范围内呈线性关系 ;表观摩尔吸光系数为 8 7× 10 3L·mol-1·cm-1,相对标准偏差为 1 2 2 % (n =6) ,回收率符合要求。     

Luminescence and Energy Transfer in Frozen Solutions of Uranyl Sulfate in Selective Excitation

Luminescence spectra of vitrified solutions of uranyl sulfate in a concentrated sulfuric acid are investigated in the range 4.2–80 K in selective laser excitation. It is shown that the luminescence spectra are a superposition of two components — the component that is related to the resonance excitation of uranyl complexes and the component that is caused by the luminescence of uranyl complexes sensitized by the transfer of electron-excitation energy from the resonance-excited centers. The nonselective character is established for the spectral migration of electron-excitation energy with participation of the bending vibrations of the uranyl complex that ensure direct vibrational transitions between neighboring electronic energy levels. The temperature evolution of the luminescence spectra can be described within the framework of the model of configuration coordinates with allowance for only the linear terms of vibronic interaction.     

基于电荷转移过程的PAN-C60共聚物薄膜的时间分辨荧光研究

利用吸收光谱和皮秒时间分辨荧光研究PAN－C60星状共聚物的电荷转移过程。PAN－C60共聚物的吸收和荧光光谱结果显示共聚物中存在着电荷转移过程。时间分辨荧光结果表明PAN的荧光衰减遵循双指数衰减规律（一快过程160ps和一慢过程1500ps)，快衰减过程主要来源于聚合物中主链间相互作用产生的空间间接极化子对的影响，慢变过程主要来源于单重态激子的辐射跃迁弛豫。在共聚物中，C60分子的存在除导致PAN激发态寿命缩短外，还影响聚合物链间的相互作用，C60分子对PAN荧光猝 灭作用主要通过慢变过程影响的，而对PAN的空间极化子对的影响主要与其快衰减过程有关。     

MAPbI3-xBrx钙钛矿薄膜中溴梯度对界面电荷转移的促进作用

混合卤素钙钛矿由于具有优异的光物理性质成为了光电子领域应用中的明星材料. 因此,钙钛矿材料中光生载流子动力学的探究和调控对于进一步提升材料的性能具有重要意义. 本文通过表面离子交换法制备了具有溴梯度的MAPbI_3-xBr_x钙钛矿薄膜,并对其内部载流子传输及界面电荷转移动力学过程进行了系统的研究. 在MAPbI_3-xBr_x薄膜中,溴离子梯度分布所导致的能带梯度能有效促进光生空穴在薄膜内部的传输过程及在界面的提取过程. 同时,由于卤素离子交换的后处理方法对薄膜表面起到了修饰作用,薄膜界面处的本征电子转移速率也得到了显著的提升. 研究表明,在通过表面后处理方法制备的混合卤素钙钛矿薄膜中,有可能同时实现界面电子和空穴转移速率的提升,这对于进一步提升钙钛矿太阳能电池的能量转换效率具有一定的启发作用.     

侧链结构对PPV/C_(60)组合体系的激发传递和电荷转移过程的影响

本文考察不同的侧链长度对聚对苯乙炔 (PPV)衍生物的光学性质等的影响 ,以及PPV/C60 的组合薄膜中的激发传递和电荷转移过程。结果表明随着连接在PPV的侧链长度的增长 ,其π π 跃迁带隙变窄 ,使得吸收和发射峰的位置逐渐红移 ;同时观测到PPV/C60 间存在着极有效的激发传递过程 ,从而使得PPV衍生物的荧光在很大程度上被C60 分子所猝灭 ;MD PPV/C60 组合膜中观测到了C-60 的吸收峰 ,这表明该体系存在着基态电荷转移过程 ,同时也表明PPV衍生物与C60 分子间的相互作用和PPV的侧链长短密切相关。