一种新型稀土配合物Eu(TTA)2(N-HPA)Phen的发光特性研究

合成了一种新的含有3个配体的稀土配合物Eu（TTA）2（N-HPA）Phen（TTA-噻吩甲酰基三氟丙酮，N—HPA=N-苯基邻氨基苯甲酸，phen=邻菲咯啉）。将稀土配合物作为掺杂物与基质PVK按照不同质量比混合共溶，旋涂成膜。通过荧光光谱，分析了薄膜的发光特性，并将其应用于有机电致发光。研究了PVK和Eu（TTA）2（N—HPA）Phen之间的能量传递，并且制备了发光层为PVK：Eu（TTA）2（N—HPA）Phen，结构为ITO／PVK：Eu（TrA）2（N—HPA）Phen／BCP／Alq3／Al的多层器件，发现改变PVK和稀土配合物的掺杂比，可以不同程度地抑制PVK的发光，最终得到纯的Eu^3＋的红色发光。实验结果证明，在PVK：Eu（TTA）2（N—HPA）Phen=5：1的质量比下，从PVK到稀土配合物之间存在充分的能量传递。     

Intramolecular proton transfer induced by divalent alkali earth metal cation in the gas state

Interactions between divalent alkali earth metal (DAEM) ions M (M?Be, Mg, Ca, Sr, Ba) and the second stable glycine conformer in the gas phase, which can transfer into the ground‐state glycine‐M²⁺ (except the glycine–Be²⁺) among each corresponding isomers when these divalent metal ions are bound, are studied at the hybrid three‐parameter B3LYP level with three different basis sets. Proton transfers from the hydroxyl to the amino nitrogen of the glycine without energy barriers have been first observed in the gas phase in these glycine–M²⁺ systems. The interaction between the glycine and these DAEM ions except beryllium and magnesium ion only create an amino hydrogen pointing to the original hydroxyl due to their weaker interaction relative to those divalent transition metal (DTM) ion‐bound glycine derivatives, being obviously different from that between the glycine and DTM ions, in which two amino hydrogens point to the original hydroxyl oxygen when these metal‐chelated glycine derivatives are produced. The interaction energy between the glycine and divalent magnesium would be the boundary of one or two amino hydrogens pointing to the hydrogyl oxygen, i.e., the ?170.3 kcal/mol of binding energy is a critical point. Similar intramolecular proton transfer has also been predicted for those DTM ion‐chelated glycine systems; however, that in the gas state has not been observed in the monovalent metal ion‐coordinated glycine systems. The binding energy between some monovalent TM ion and the glycine is similar to that of the glycine–Ba²⁺, which has the lowest binding strength among these DAEM–ion chelated glycine complexes. The difference among them only lies in the larger electrostatic and polarized effects in the latter, which favor the stability of the zwitterionic glycine form in the gas phase. According to these observations, we predict that the zwitterionic glycine would exist in the field of two positive charges in the gas phase. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 205–214, 2003     

Chemical equilibrium model for the thermodynamic properties of mixed aqueous micellar systems: Application to thermodynamic functions of transfer

Mixed micelles can be formed in water between various pairs of hydrophobic solutes such as surfactants, alcohols and hydrocarbons. These systems can often be studied through the thermodynamic functions of transfer of one of the solutes, usually kept near infinite dilution, from water to an aqueous solution of the other solute. When mixed micelles are formed, these functions change significantly, and often go through extrema, in the region where the binary system micellizes or undergoes some microphase transition.Three main effects are responsible for the observed trends: pair-wise interactions between both solutes in the monomeric form, a distribution of the reference solute between the aqueous and micellar phases and a shift in the monomer-micelle equilibrium in the vicinity of the reference solute. Simple equations can be derived for these three effects which can account for the sign and magnitude of the observed trends using parameters which are derived for the most part from the two binary systems.     

Second-order Green's function calculations of the ionization potential of a (H2)7 chain embedded in a homogeneous electric field

Summary The vertical ionization potential and the related pole strength of a model alternant chain of 14 hydrogen atoms subject to a homogeneous electric field, parallel to the chain and of increasing intensity are calculated, in the framework of a 6–31G** basis set, at the second-order level of the many-body Green's function theory. Trends observed with orbital relaxation, pair removal and pair relaxation effects are interpreted in terms of deformations of the electron density.     

高能量密度材料1,3,3-三硝基氮杂环丁烷研究进展

介绍了新型高能量密度材料1，3，3－三硝基氮杂环丁烷（TNAZ）的合成，物理性能，爆轰性能，安全性，热分解机理及其应用研究的进展， 并对其应用前景进行了展望。     

The initial oxidation of magnesium: an in situ study with XPS,HERDA and ellipsometry

The initial oxidation of magnesium at oxygen partial pressures between 1.3 × 10^?8 and 1.3 × 10^?5 Pa and at temperatures ranging from 273 to 550 K has been investigated in situ with X‐ray photoelectron spectroscopy (XPS), ellipsometry and high resolution elastic recoil detection analysis (HERDA). Quantitative analysis of the XPS spectra showed a clear oxygen deficiency with respect to MgO for the initial oxide. HERDA measurements confirmed this relatively low oxygen content in the thin oxide layers formed. Ellipsometry measurements showed that the electronic structure of the initially formed oxide differs significantly from that of bulk MgO. The band gap values at room temperature for the oxide layers investigated are clearly smaller than the value for bulk MgO. Copyright © 2006 John Wiley & Sons, Ltd.     

(BN)_n团簇的结构和稳定性

用HF方法、密度泛函理论的B3LYP以及微扰理论的MP2方法 ,在 6 3 1G(d)基组水平上 ,对 (BN) n(n =1～ 16)团簇的各种可能结构进行了优化 .讨论了环状与笼状稳定团簇的几何构型、自然键轨道 (NBO)、振动频率、结合能、核独立化学位移 (NICS)和能量二次差分 ,得到了 (BN) n(n =1～ 16)团簇结构的稳定性信息 .比较了HF ,B3LYP以及MP2三种理论方法对(BN) n 团簇的适应性所表现出的差异 .     

A Structural Basis of Light Energy and Electron Transfer in Biology (Nobel Lecture)

Aspects of intramolecular light energy and electron transfer are discussed for three protein cofactor complexes whose three-dimensional structures have been elucidated by X-ray crystallography: the light harvesting phycobilisomes of cyanobacteria, the reaction center of purple bacteria, and the blue multi-copper oxidases. A wealth of functional data is available for these systems which allows specific correlations to be made between structure and function and general conclusions to be drawn about light energy and electron transfer in biological materials.     

The Wave Function with Symplectic Symmetry and Its Application

The antisymmetrized geminal power (AGP) and sequential product of geminals(SPG) functions, the basis functions with symplectic symmetry, are linearly combined to calculate the ground state of the LiH molecule. The calculation results show that the AGP or SPG function gives the same ground state results as the linear combination.     

非晶高聚物对聚(ε-己内酯)在其与苯乙烯-丙烯腈共聚物相容共混物中球晶生长速率的影响

本文研究了聚(ε-己内酯)(PCL)在其与苯乙烯-丙烯腈共聚物(SAN)的相容共混物中球晶生长速率与共混组成和结晶温度的关系.发现聚己内酯的球晶生长速率随着SAN的含量增加而下降.由于PCL与SAN是相容共混物,因此在用二次成核动力学方程描述PCL球晶生长速率时,我们引进了相互作用参数X.结果由共混体系的结晶动力学方程计算到的X值与由平衡熔点下降方法计算到的X_(23)值是相同的;而PCL晶体的折叠表面自由能则随着SAN含量的增加而下降.这些结果说明非晶高聚物SAN有碍于PCL球晶的生长.