Spectroscopic Studies on Charge Transfer from Ce~(3 ) to Yb~(3 ) in KMgF_3∶Ce,Yb Nanocrystals

Nanocrystals of KMgF3 single-doped and codoped with Ce3 or/and Yb3 were synthesized separately by the microemulsion method.The X-ray diffraction(XRD)patterns were indexed to show that the KMgF3 crystal system was unchanged.The fluorescent spectra of KMgF3∶Ce,Yb polycrystal powders were studied and compared with those of the Ce,Yb doped KMgF3 crystals produced using the high-temperature solid phase method.The diffuse reflection spectra and infrared emission of KMgF3∶Ce,Yb were investigated.From the results,the authors could confirm that there were charge transfer processes from Ce3 to Yb3 in both KMgF3∶Ce,Yb nanocrystals and polycrystal powders.     

KMgF3∶Ce^3＋,Eu^2＋的溶剂热合成与光谱性质

采用溶剂热法合成了Eu^2＋,Ce^3＋单掺和双掺KMgF3。分析了样品的结构与形貌。结果表明,所合成的样品均为单相,颗粒粒度分布集中。测定了它们的激发和发射光谱,结果显示：在单掺Eu^2＋的KMgF3中,没有观察到位于420nm附近由微量氧色心引起的宽带发射,只发现峰值位于360nm附近的锐峰线发射,说明溶剂热合成的KMgF3∶Eu中氧含量极低;在KMgF3双掺体系中由于Eu^2＋和Ce^3＋竞争吸收激发能,Eu^2＋把能量传递给Ce^3＋,存在Eu^2＋→Ce^3＋能量传递过程,观察到Ce^3＋的较强的发射带和Eu^2＋的较弱的线发射,并讨论了能量传递机理。     

Zircon Ce^4＋/Ce^3＋ Ratios of the Tongchang Intrusions in Jinping County, Yunnan Province： Implications for Mineralization

对金沙江—红河成矿带南段铜厂斑岩铜钼矿区含矿的石英正长斑岩和无矿的细粒正长岩开展了锆石的Ce^4＋/Ce^3＋比值、δCe及δEu值的研究,结果显示含矿的4个石英正长斑岩样品的锆石Ce^4＋/Ce^3＋比值变化范围为208～336,平均比值为265,δCe值变化范围为17.6～60.6,平均值为33.8,δEu值变化范围为0.592～0.628,平均值为0.611,不含矿的1个细粒正长岩样品的锆石Ce^4＋/Ce^3＋比值为61,δCe值为8.50,δEu值为0.424,含矿的石英正长斑岩的锆石Ce^4＋/Ce^3＋比值、δCe及δEu值均明显高于不含矿的细粒正长岩,反映了与成矿有关的岩浆具有相对高的氧化状态。对比金沙江—红河成矿带北段的玉龙斑岩铜钼矿带和中段的马厂箐斑岩铜钼矿的含矿与无矿岩体,它们的锆石Ce^4＋/Ce^3＋比值与南段铜厂斑岩铜钼矿含矿及无矿岩体具有基本类似的特征,含矿岩体的锆石Ce^4＋/Ce^3＋比值通常大于200,而不含矿岩体的锆石Ce^4＋/Ce^3＋比值基本上都小于120。这种差异对进一步认识金沙江—红河成矿带斑岩铜钼矿的岩浆氧逸度特征具有重要的理论意义,对斑岩铜钼矿的找矿工作具有一定的指导意义。     

Studies on Upconversion Mechanism of ZrO2 ： Er^3＋, Yb^3＋ Nanocrystals Under Excitation at 488 and 980 nm

Erbium, Ytterbium-codoped ZrO2 nanoparticles(ZrO2:Er^3 ,Yb^3 ) were prepared by the sol-emulsiongel technique. The purpose of the present study is the application of upconversion phosphor in the biological label. In order to make out the mechanism of upconversion under 980 nm excitation the 488 nm pump was used. The influence of temperature on the crystallite phase was studied. The results confirm the upconverted mechanism in ZrO2:Er^3 ,Yb^3 nanocrystals is due to an energy transfer upconversion(ETU).     

Growth and Spectroscopic Characteristics of Yb3＋：LiGd（WO4）2 Crystal

The Yb3+:LiGd(WO4)2 crystal with the dimension of Φ15×35 mm3 was grown by Czochralski technique. The spectroscopic characterization and fluorescence dynamics of Yb3+ in Yb3+:LiGd(WO4)2 crystal were investigated. The Yb3+:LiGd(WO4)2 crystal exhibits a broad absorption band centered near 975 nm with the linewidths of 16 and 11 nm and maximal absorption cross-section of 3.60 × 10-20 and 2.90 × 10-20 cm2 for π- and σ-polarization, respectively. The emission broadband has an FWHM of 47 and 45 nm with the emission cross sections of 3.92 × 10-20 and 3.34 × 10-20 cm2 at 1020 nm for π- and σ-polarization, respectively. The measured fluorescence lifetime is 398 μs. The blue light emission around 480 nm through cooperative upconversion from the de-excitation of excited Yb3+-Yb3+ pairs at 4 K was observed under 932-nm excitation and demonstrated.     

KMgF3：Eu,X（X=Ce,Cr,Gd,Cu）体系中Eu^2＋振动光谱和共掺离子的格位取代

测定了一系列单掺杂Eu^2 和双掺杂Eu,X(X=Ce,Cr,Gd,Cu）的KMgF3晶体在300K和77K的高分辨发射光谱以及伴随的振动光谱。据此研究了Eu^2 在这些体系中的振动跃迁特征,并指认了每一振动峰所对应的正则振动模式。首次发现了在共振杂体系中Eu^2 振动频率与其它掺杂离子格位取代间的相关性。     

杂质的添加对SrAl2O：Eu^2＋,Dy^3＋余辉发光特性的改善

采用溶胶－凝胶法制备SrAl2O4:Eu^2 ,Dy^3 磷光体,并在合成过程中添加硼或硅以探讨光致发光及长余辉发光性质。发现硼、硅添加物不仅是助熔剂,且能改良SrAl2O4:Eu^2 ,Dy^3 之长余辉的持续时间及余辉发光强度。基于不同磷光体样品的实验结果比较,综合材料表面微结构观察、X射线衍射图谱、热释发光光谱与余辉衰减曲线的测量等实验结果分析,推断在SrAl2O4:Eu^2 ,Dy^3 中添加硼、硅可导致磷光体缺陷增加并稳定活化剂Eu^2 的价态。     

KZnF3中Ce3+→Eu2+的能量传递

研究了KZnF3中Ce3+和Eu2+的光谱特性,在共掺Ce3+和Eu2+的体系中,观察到了Ce3+对Eu2+的能量传递过程.计算了能量传递的量子效率,探讨了能量传递机理.研究发现,Ce3+的存在有利于Eu2+的f-f跃迁线状发射.     

有机半导体材料中的电荷转移

在介绍有机半导体材料电荷转移基本理论的基础上,对利用电荷转移研究有机半导体材料的导电、光电导和发光过程的现状进行评述,认为电荷转移是有机半导体材料研究的关键问题,开展其研究不仅有助于弄清一些新现象、新效应的物理起因,还可望找到预测有机半导体材料相关性能的有效手段.     

联吡啶钌配合物[Ru(Htcterpy)X3]3-[X=NCS,CN,Cl]的电子结构和光谱性质的理论研究

利用DFT中的B3LYP方法优化了3个联吡啶钌配合物[Ru(Htcterpy)X3]3-[tcterpy=4,4',4"-tricarboxy-2,2'∶6',2"-terpyridine, X=NCS(1), CN(2), Cl(3)]的基态几何结构, 得到的几何参数与实验结果吻合得很好. 采用TD-DFT方法, 得到了配合物1~3在气态和溶液(乙醇溶液和水溶液)中的激发态电子结构和电子吸收光谱. 利用SCRF方法中的CPCM模型来模拟溶剂化效应. 研究结果表明, 配合物1~3在气态和溶液中的吸收跃迁性质相似, 低能吸收均被指认为MLCT和LLCT的混合跃迁, 高能吸收均被指认为三联吡啶配体内的π→π*跃迁. 溶剂化效应使配合物1~3在溶液中的吸收光谱蓝移.     

Optical Spectroscopy Properties of KMgF3 ：Eu^2＋ Nanocrystals and Powder Synthesized by Microemulsion and Solvothermal Process

IntroductionPerovskite complex fluorides have attracted great ainterest due to their particular physical properties, suchas piezoelectric characteristics[1], ferromagnetic prop-erty[2], nonmagnetic insulator behavior[3], and photo-luminescence host functi…     

The Charge Transfer Complex between 2, 3-diamino-5-bromopyridine and Chloranilic acid: Preparation,Spectroscopic Characterization,DNA binding,and DFT/PCM analysis

A charge transfer hydrogen bonded complex was prepared and experimentally explored in an acetonitrile (ACN) medium between the proton acceptor (electron donor) 2, 3-Diamino-5-bromopyridine and the proton donor (electron acceptor) chloranilic acid. The stoichiometry of the charge transfer complex is 1:1. The Benesi-Hildebrand equation is used to calculate the molar absorptivity (ε_CT), association constant (K_CT) and other spectroscopic physical characteristics. The solid compound was synthesized and studied using several spectroscopic methods. The presence of charge and proton transfers in the resultant complex was supported by ¹H NMR, FT-IR and SEM-EDX investigations. The complex DNA binding ability was investigated using electron absorption spectroscopy, and the CT complex binding mechanism is intercalative. The intrinsic binding constant (K_b) value is 5.2 × 10⁶M?1. The good binding affinity of the CT complex makes it potentially suitable for usage as a pharmaceutical in the future. Molecular docking calculations have been performed between CT complex and DNA (ID = 1BNA) to study the CT-DNA interaction theoretically. To corroborate the experimental findings, calculations based on DFT were carried out in the gas and PCM analysis where the existence of charge and hydrogen transfers. Finally, good agreement between experimental and theoretical computations was observed confirming that the basis set used is appropriate for the system under examination.     

含纳米晶颗粒的Yb3+/Er3+共掺透明碲酸盐玻璃陶瓷的光谱性质研究

在组成为15Li2O-15Nb2O5-70TeO2-0.1Er2O3-0.4Yb2O3（%, 摩尔分数）的碲酸盐玻璃基础上, 采用两步热处理法制备了透明的含纳米晶颗粒碲酸盐玻璃陶瓷. 通过X射线衍射（XRD）测试表明, 玻璃陶瓷中的晶体颗粒组成为Yb6Te5O19.2或Er6Te5O19.2, 晶粒尺寸约为55 nm. 根据Judd-Ofelt理论计算了Er^3＋离子在基质玻璃和玻璃陶瓷中的光谱参数Ωt（t＝2, 4, 6）以及Er^3＋：4I15/2→4I13/2跃迁自发辐射几率, 根据McCumber理论计算了Er^3＋：4I13/2→4I15/2跃迁的发射截面. 测试了基质玻璃和玻璃陶瓷的拉曼光谱, 对比研究了铒离子在基质玻璃和玻璃陶瓷中1.5 μm处荧光和上转换光谱特性.     

Electron Transfer and Charge Transfer: Twin Themes in Unifying the Mechanisms of Organic and Organometallic Reactions

The broad varieties of organic and organometallic reactions merge into a common unifying mechanism by considering all nucleophiles and electrophiles as electron donors (D) and electron acceptors (A), respectively. Comparison of outer-sphere and inner-sphere electron transfers with the aid of Marcus theory provides the thermochemical basis for the generalized free energy relationship for electron transfer (FERET) in Equation (37) and its corollaries in Equations (43) and (44) that have wide predictive applicability to electrophilic aromatic substitutions, olefin additions, organometallic cleavages, etc. The FERET is based on the conversion of the weak nucleophile–electrophile interactions extant in the ubiquitous electron donor—acceptor (EDA) precursor complex [D, A] to the radical ion pair [D^⊕, A^?], for which the free energy change can be evaluated from the charge-transfer absorption spectra according to Mulliken theory. FERET analysis thus indicates that the charge-transfer ion pairs [D^⊕, A^?] are energetically equivalent to the transition states for nucleophile/electrophile transformations. The behavior of such ion pairs can be directly observed immediately following the irradiation of the charge-transfer bands of various EDA complexes with a 25-ps laser pulse. Such studies confirm the radical ion pair [Arene^⊕, NO₂] as a viable intermediate in electrophilic aromatic nitration, as presented in the electron-transfer mechanism between arenes and the nitryl cation (NO) electrophile.     

球烯C60与锌酞菁形成电荷迁移络合物的研究

球烯是一种很有前途的新型非线性光学材料，它具有非平面的共轭离域大Π键体系，具有结合电子的能力，可作为电子受体与电子给体形成电荷迁移络合物（CTC），并能改善有机分子的光学和电学性质[1~4]．金属酞青（MPc）也具有共轭大Π键体系，富有π电子，且具有良好的光敏性、化学稳定性及热稳定性．在一定条件下，球烯与金属酞育形成的CTC将大大改善金属酞育的光电性能．因此，研究球烯与金属酞蓄形成的CTC对开拓球烯与金属酞警的应用有重要意义．本文根据C60与锌酞菁（ZnPc）形成的CTC的光谱特征对其组成及相应的平衡常数进行了研究…