Effect of varying lanthanide local coordination sphere on luminescence properties illustrated by selected inorganic and organic rare earth complexes synthesized in sol-gel host glasses

Inorganic and organic ligands were carefully selected to illustrate the effect of modifications in the local field environment around the rare earth lanthanide (III) on its emission properties. In this article two strategies were employed to enhance emission of lanthanides encapsulated in sol-gel glass. (i) Changing the symmetry around the lanthanide, which was diagnosed by changing the local environment around the lanthanide using different inorganic counter ions (acetate, nitrate and chloride) these ligands differ in their affinity toward the lanthanide first coordination sphere. The ligand that penetrates the lanthanide more results in more asymmetric environment and thus results in higher emission. The aim of this part was to demonstrate the change of symmetry on emission in the absence of energy transfer. Our results indicate that the acetate ion has the highest affinity toward the first coordination sphere followed by the nitrate while the chloride showed the lowest affinity. Penetration by the ligands ofthe lanthanide also results in removing OH quenchers surrounding the lanthanide and this further explains the boost in emission. (ii) A bulky organic ligand that forms a complex with the lanthanide is used. The organic ligand separates the lanthanide ion from inner O-H oscillators. In this case the chelating organic chromophore with suitable photophysical properties was employed to sensitize the lanthanide and thus energy transfer occurs via the antenna effect. The organic ligand absorbs UV light, then energy is transferred to the lanthanide and finally the lanthanide emits in the visible region. The first coordination environment surrounding europium was controlled by the ligand selection and the outer sphere was modified by doping the synthesized complexes in an optically transparent sol-gel glass host. The glass network carefully prepared by sol-gel process is effective in preventing free oxygen and water from attacking lanthanide -complexes without loss of luminescence. Emission spectroscopy measurements of the doped silica specimens confirmed the variation of Eu (III) emission depending on the first coordination sphere surrounding the europium ion. The encapsulation of the europium complexes was performed for two reasons: (i) to improve the stability of red phosphor with efficient and high color-purity characteristics under ultraviolet excitation and (ii) this work provides a framework for preparing transparent composite glasses that are robust hosts to study the fundamental interactions between nano-materials and light.     

参外联合激励复合非线性振子的分岔分析

讨论了参外联合激励复合非线性振子的动力学行为.对其定常解在一阶近似下的方程进行了局部分岔分析,给出了简单分岔和Hopf分岔发生的条件,并通过对近似方程和原系统的数值模拟加以验证.分析了多种参数对该振子动力学行为演化过程的影响.根据全局分岔理论探讨了该振子在不同条件下发生同宿、异宿分岔的必要条件,其结论与数值计算的结果大致符合. 关键词： 复合非线性振子 局部分岔 全局分岔 混沌     

射频溅射法制备Pb_(1-x)Co_xSe薄膜及物性研究

利用复合靶共溅射法制备了半磁性半导体 Ｐｂ１－ ｘ Ｃｏｘ Ｓｅ 薄膜．研究了薄膜的成分结构以及电阻率温度特性和磁化率温度特性间的关系．结果表明：由于 Ｃｏ 离子介入, Ｐｂ１－ ｘ Ｃｏｘ Ｓｅ 发生了由金属特性向半导体特性的转变,在充分低的温度下,并伴有磁相转变．磁相转变温度与磁性离子浓度相关,磁化率的相对变化幅度与磁性离子浓度有关     

Strategic commitment to price to stimulate downstream innovation in a supply chain

It is generally in a firm’s interest for its supply chain partners to invest in innovations. To the extent that these innovations either reduce the partners’ variable costs or stimulate demand for the end product, they will tend to lead to higher levels of output for all of the firms in the chain. However, in response to the innovations of its partners, a firm may have an incentive to opportunistically increase its own prices. The possibility of such opportunistic behavior creates a hold-up problem that leads supply chain partners to underinvest in innovation. Clearly, this hold-up problem could be eliminated by a pre-commitment to price. However, by making an advance commitment to price, a firm sacrifices an important means of responding to demand uncertainty. In this paper we examine the trade-off that is faced when a firm’s channel partner has opportunities to invest in either cost reduction or quality improvement, i.e. demand enhancement. Should it commit to a price in order to encourage innovation, or should it remain flexible in order to respond to demand uncertainty. We discuss several simple wholesale pricing mechanisms with respect to this trade-off.     

Evaluating Individual Market Power in Electricity Markets via Agent-Based Simulation

We use agent-based simulation in a coordination game to analyse the possibility of market power abuse in a competitive electricity market. The context of this was a real application to the England and Wales electricity market as part of a Competition Commission Inquiry into whether two particular generators could profitably influence wholesale prices. The research contributions of this paper are both in the areas of market power and market design policy issues for electricity markets, and in the methodological use of large industry-wide evolutionary simulation models.     

On the Application of the Auxiliary Problem Principle

The auxiliary problem principle (APP) derives from a general theory on decomposition-coordination methods establishing a comprehensive framework for both one-level and two-level methods. In this paper, the results of the two-level methods of APP are specialized for an efficient application to some engineering problems.     

Theorems of Large Deviations in the Approximation by the Compound Poisson Distribution

The paper is devoted to the research of large deviation probabilities in the approximation by compound Poisson law.     

Evolutionary insights on the willingness to communicate

While in previous models of pre-play communication players are forced to communicate, we investigate what happens if players can choose not to participate in this cheap talk. Outcomes are predicted by analyzing evolutionary stability in a population of a priori identical players. If the game following the communication rewards players who choose the same action then an efficient outcome is only guaranteed when participation in the pre-play communication is voluntary. If however players aim to coordinate on choosing different actions in the underlying game and there are sufficiently many messages then the highest payoff is selected when players are forced to talk to each other before playing the game. Received: September 2000/Revised: March 2003     

二茂铁有机锡衍生物的13C,119Sn NMR研究

本文测定了几种二茂铁有机锡衍生物的¹¹⁹Sn,¹³C NMR谱。对其中几种衍生物的¹³C NMR谱进行了归属,从而进一步验证了这类化合物的结构。着重讨论了结构如化合物中取代基X的改变对¹¹⁹Sn化学位移的影响。并对结构如 类化合物N→Sn异侧配位的问题进行了讨论。     

一个二维梯状化合物[Ni(μ1，5-dca)2(en)]n的合成，结构和磁性(英)

A new nickel(Ⅱ)-dicyanamide compound, [Ni(dca)₂(en)]_n (1) (dca=dicyanamide anion, [N(CN)₂]^-); en=ethylene diamine), has been synthesized and its structure has been determined by single crystal X-ray diffraction analysis. The crystal is monoclinic, space group P2₁/n with unit cell dimensions: a=0.694 3(1) nm, b=1.041 5(2) nm, c=1.4132(2) nm, and β=90.381°, Z=4, V=1.011 0(3) nm³. In this compound, the adjacent nickel atoms are connected by dca all in μ_1，5-bridging mode to form ladder-like units, which are linked with double dca bridges to generate a regular infinite stair-like structure. Temperature-dependent magnetic susceptibility was also characterized for this compound. CCDC: 208276.