光致分子间电子转移-受体分子结构对转移速率的影响（英文）

本文利用超快时间分辨瞬态光栅光谱技术研究了受体分子结构对光致分子间电子转移速率的影响,以罗丹明101和罗丹明6G在苯胺中的溶液作为研究样品.苯胺到两种染料分子之间的前向电子转移时间常数以及后续的从染料分子到苯胺的反向电子转移时间常数可以被测得.结果表明无论是前向电子转移还是反向电子转移,罗丹明6G都较罗丹明101进行得更快.通过量子化学计算以及后续分析,发现更具柔性的罗丹明6G分子和苯胺之间具有更强的分子间电子耦合从而导致更大的分子间电子转移速率.     

碳量子点/罗丹明B分子复合体系中的能量和电子转移过程研究

本文采用荧光光谱结合稳态和瞬态吸收光谱技术,研究了碳量子点(CQDs)/罗丹明B(RhB)分子复合体系o-CQDs/RhB和m-CQDs/RhB中的能量转移和电子转移过程以及它们之间的关系. 研究发现在能量转移效率为73.2%的o-CQDs/RhB体系中,电子转移过程可以忽略;而在能量转移效率低于33.5%的m-CQDs/RhB体系中,电子转移过程则较为显著. 在这个由碳量子点和染料分子组成的典型复合体系中所揭示的能量转移与电子转移过程之间的内联关系,将为与激子猝灭相关的应用提供有用的视角.     

调制光/电作用下染料敏化太阳电池中电荷传输和界面转移研究

详细讨论了染料敏化太阳电池(DSC)在稳态光照射或外加偏压下电荷的传输和转移过程,以及在调制光/电作用下电池的频率响应特点.通过电化学阻抗谱、光电化学阻抗谱、强度调制光电流谱和强度调制光电压谱等四种频谱光电测试手段,对DSC中TiO₂薄膜电子传输和界面转移的相关时间常数进行测量.详细分析和比较了电荷的传输及转移过程对时间常数的影响.结果表明,在低光强或低偏压下电荷传输和转移过程对时间常数影响较小,但在高光强或高偏压下对电子寿命影响明显.     

光诱导呫吨酮电子转移和氢转移反应的激光闪光光解研究

用时间分辨激光闪光光解的方法研究了在乙腈溶剂中呫吨酮的激发三重态的性质，并得到了呫吨酮激发三重态和胺类、醇类以及酚类反应的瞬态吸收光谱和猝灭速率常数(kq)．除了苯胺和3-硝基苯胺被认为是能量转移外，呫吨酮和其余胺类的反应随着自由能变的减校lgkq逐渐增大，由此认为发生了电子转移反应．而对于二甲基-对甲苯胺、3,5,N,N-四甲基苯胺、N,N-二甲基苯胺、三乙胺来说，通过瞬态吸收光谱的变化可以知道既有电子转移反应又有氢转移反应发生．呫吨酮和醇类只发生氢转移反应，其猝灭速率常数和醇的?-C?H的键能有关．由     

激光闪光光解研究二羟基蒽醌和腺嘌呤/胞嘧啶的电子转移反应

采用纳秒时间分辨的激光闪光光解技术研究了乙腈/水混合溶液中二羟基蒽醌和腺嘌呤或胞嘧啶之间的电子转移反应. 在355 nm紫外光作用下,经由系间窜跃产生的三重态二羟基蒽醌与两碱基分别发生电子转移反应,其中碱基作为典型的电子给体. 基于测量到的反应瞬态中间体的动力学淬灭速率,两个反应过程被认为分步进行,先电子转移之后发生质子转移反应. 通过研究表观淬灭速率与两个碱基浓度的依赖关系,分别得到了两个双分子间电子转移反应的速率常数,分别是9.0×10⁸ L/(mol·s) (胞嘧啶)、3.3×10⁸ L/(mol·s) (腺嘌呤).     

异质结中桥分子电子转移的飞秒激光控制研究

以染料分子通过桥分子吸附在半导体表面所组成的异质结为研究对象, 用一维约化振动模型研究了异质结中桥分子电子转移的飞秒激光优化控制过程,分别对单个桥分子和两个并列桥分子连接的异质结系统的电子传输及飞秒激光控制做了仔细的计算和讨论,理论上分析了桥分子的存在对异质结中超快电子转移路径的影响. 关键词： 飞秒激光 优化控制 异质结电子转移     

超快时间分辨多元瞬态光栅光谱实验

简述了超快时间分辨多元瞬态光栅光谱的实验原理、装置和光路图,观测了多元瞬态光栅在Rhodamine 6G(Rh6G+)/N,N-diethylaniline(DEA)体系中的超快光致电子转移的物理过程.实验结果表明:使用超快时间分辨多元瞬态光栅光谱技术在440nm处得到的DEA+动力学很好地描述了从DEA+到Rh6G+*的前向电子转移.     

虚时间分裂算符方法研究溶剂电子转移动力学

在Sumi-Marcus理论中，采用虚时间分裂算符方法研究电子转移动力学．此方法具体应用于计算嗪-1和N,N-二甲基苯胺分子之间的电子转移速率常数．通过计算得到的两种反应物态的平均速率常数和一个长时间的速率常数，揭示了不同的sink函数时的电子转移动力学．在数值模拟过程中还发现了一些新的电子转移特性．     

十二烷基苯磺酸钠胶束中吖啶橙与罗丹明6G间的能量转移机理研究

以吖啶橙(AO)与罗丹明6G(R6G)为例讨论了胶束介质中碱性荧光染料间相互作用的机理。在十二烷基苯磺酸钠水溶液中,吖啶橙与罗丹明6G染料分子间相互作用发生有效能量转移。在不同温度下,通过对能量转移体系研究,初步证明吖啶橙与罗丹明6G间发生能量转移引起吖啶橙的荧光猝灭为静态猝灭过程。通过热力学参数的计算,得出能量转移体系的结合力主要为静电引力。同时也对转移体系的能量转移效率,结合位点数和结合距离进行了计算。     

罗丹明101染料的光谱特性研究

观测了罗丹明101染料在甲醇和酸性甲醇溶液巾的稳态吸收、稳态荧光和时间分辨荧光光谱,得到了吸收与荧光光谱的特征信息以及荧光寿命;通过拉曼光谱、红外光谱和密度泛函理论计算,对罗丹明101染料分子的振动模式进行了指认.研究结果全面系统地表征了罗丹明101染料的光谱特征以及分子结构和振动信息,为罗丹明101染料在染料敏化太阳能电池和生物荧光标记等方面的应用研究提供了依据.     

Transfer ionization of the isocharge sequence ion and Ar collisions

The ratios of transfer ionization to single capture for isocharge C^{q+}, N^{q+}, O^{q+}, Ne^{q+} ions on Ar atoms are measured by using position-sensitive and time-of-flight techniques. It is found that the ratio R_{1} increases with nuclear charge Z in a q=4 sequence, and the ratio R_{1} sequences have the minimum values at Z=7 and Z=8 in q=5 and q=6 sequences, respectively, and the ratio R_{1} decreases with the increase in the nuclear charge Z in a q=7 sequence. The results may be explained within the frame of the statistical model. It may be concluded that the transfer ionization depends remarkably upon the electronic structure of the projectile. The projectiles used in this study have the same charge state and velocity, but different electronic structures. The dependence of the ratio R_{1} on q is studied for Ne^{q+}-Ar collisions. The ratio R_{1} is found to increase as q increases for Ne^{q+}－Ar collisions. The measured dependence of the ratio R_{1} on q is compared with the calculation using the molecular Coulomb over-barrier model.     

掺杂PPQ薄膜的电致发光及电场调制

从掺杂PPQ薄膜单层器件的电致发光光谱在掺杂前后的变化。说明掺杂PPQ薄膜中存在着基质分子和掺杂分子间的能量传递，其电致发光光谱随加电场变化说明电场对PPQ薄膜的电致发光具有调制作用。用一个由单链模型扩展到包括杂质和外场的Hamiltonian进行数值求解。结果表明：在PPQ和TPL分子之间有效的能量传递是源于它们之间的是荷转移，且随着外加电压的变化，其电致发光谱峰位的移动与掺杂前后系统总量的改变及发光强度与掺杂后转移的电荷数之间分别存在对应关系，这一模型很好地解释了电场对PPQ薄膜电致发光的调制作用。     

A mechanistic dichotomy in concerted versus stepwise pathways in hydride and hydrogen transfer reactions of NADH analogues

A mechanistic dichotomy of one‐step versus stepwise pathways in hydride and hydrogen transfer reactions of NADH analogues is discussed including the relation between two pathways: a continuous change versus a discontinuous change of the mechanism. Examples of stepwise electron–proton–electron transfer through a charge transfer (CT) complex in hydride transfer from NADH analogues to hydride acceptors are presented including the detection and the reactivity of the intermediate, that is, radical cations of NADH analogues. The relation between stepwise versus one‐step mechanisms of hydride and hydrogen transfer reaction of NADH analogues is also clarified by showing examples of the change of the mechanism including the borderline. Copyright © 2008 John Wiley & Sons, Ltd.     

掺杂PVK薄膜的荧光谱及电荷转移

根据PVK掺杂后荧光谱的变化，说明掺杂PVK薄膜的电致发光存在着从基质分子向掺杂分子的能量传递，用一个由单链模型扩展到包括杂质的哈密顿量进行数值求解，结果表明：在PVK和杂质分子之间有效的能量传递是源于它僮之间的电荷转移，且随着杂质浓度的变化，其荧光谱峰位的移动与掺杂前后系统总能量的改变及荧光谱强度与掺杂后转移的电荷数之间分别存在对应关系。该模型较好地解释了有关的实验结果。     

Effect of Swirl Generator Inserted Into a Tube on Exergy Transfer: Decaying Flow

This study experimentally investigates the effect of conical injector type swirl generator inserts on heat and exergy transfer in a uniform heat flux tube for turbulence regime. One hundred twenty watts of heat are applied by coiling a flexible silicone heater on the tube (copper pipe) with an inside diameter of 62 mm and length of 1,200 mm. The conical injector type swirl generator has a conical shape, which is similar to a funnel, with angle (α) of 30°, 45°, and 60°. Circular holes are drilled on the conical injector type swirl generator as three different cross-sectional areas (A_h). The total areas (A_t = N.A_h) of the holes on the conical injector type swirl generator equal each other. Because of this, the three different holes numbers (N) are produced. Flow directors having three different angles (β = 30°, 60°, and 90°) to radial direction are attached to every one of the holes. This study is a typical example for decaying flow. Reynolds number (Re) was varied from 10,000 to 35,000, so the flow was considered as only a turbulent regime. All experiments were conducted with air accordingly; Prandtl number was approximately fixed at 0.71. The local and average heat transfer Nusselt number (Nu_h) and exergy transfer Nusselt number (Nu_e) are calculated and discussed in this article. It is found that the Nu_h increases with an increase in Reynolds number, director angle (β), and director diameter (d) but with a decrease in the conical injector type swirl generator angle (α). However, Nu_e decreases depending on the same independent parameters.     

斜翅型冷凝强化换热管传热性能的实验研究

对一种斜翅型外翅片带内螺纹的冷凝强化换热管进行传热性能的实验研究。管外冷凝换热的制冷剂为R134a,管内对流换热的介质为水。分别在定热流密度与定水流速的条件下进行一系列工况的实验,得到相应的实验数据。在定热流密度条件下,利用Wilson图解法得到管内的换热系数数据及相应的计算关联式。在定水流速的条件下,利用分离方法得到管外冷凝换热系数数据及相应的计算关联式。将强化管换热系数数据与光管换热系数的理论计算值进行了比较,结果表明:冷凝强化换热管管内对流换热的强化倍率为2.4,管外凝结换热系数随壁面过冷度的增加而增大,管外凝结换热的强化倍率为:1.78～3.92。     

Quantum Communication Through a Two-Dimensional Spin Network

We investigate the state or entanglement transfer through a two-dimensional spin network. We show that for state transfer, better fidelity can be gained along the diagonal direction but for entanglement transfer, when the initial entanglement is created along the boundary, the concurrence is more inclined to propagate along the boundary. This behavior is produced by quantum mechanical interference and the communication quality depends on the precise size of the network. For some number of sites, the fidelity in a two-dimensional channel is higher than one-dimensional case. This is an important result for realizing quantum communication through high dimension spin chain networks.     

Investigation of the transfer ionization process in collisions of partially stripped ions on He

In this paper a projectile ion-recoil ion coincidence technique is used to investigate the transfer ionization processes in collisions of 0.22--6.30~MeV C^{q + } ions and 0.25--6.35~MeV O^{q + } ions (q=1, 2, 3, 4) with the He atom separately. The cross section ratio f of transfer ionization to single electron transfer is measured, and the dependence of f on both charge state q and energy E of the projectiles is investigated. The electron-structure and the mechanisms leading to transfer ionization affect the dependence of f on q and E. Our measurements, along with other data published previously, suggest a similar dependence of f on charge state and energy of projectile for partially stripped ions over a large energy range. The maximum value of f is approximately 0.17q^{0.60}; the energy corresponding to maximum f is about 160q^{0.60}~keV/u.     

Quantum Communication Through a Two-Dimensional Spin Network

We investigate the state or entanglement transfer through a two-dimensional spin network. We show that for state transfer, better fidelity can be gained along the diagonal direction but for entanglement transfer, when the initial entanglement is created along the boundary, the concurrence is more inclined to propagate along the boundary. This behavior is produced by quantum mechanical interference and the communication quality depends on the precise size of the network. For some number of sites, the fidelity in a two-dimensional channel is higher than one-dimensional case. This is an important result for realizing quantum communication through high dimension spin chain networks.     

Efficient non-resonant intermolecular vibrational energy transfer

Molecular excited vibrational states are metastable states and we incorporate their finite lifetimes into the theory of vibrational energy transfer between weakly interacting molecules, i.e., at internuclear distances at which they do not have a chemical bond. Expressions for the effective lifetime of an initially vibrationally excited molecule in the presence of a neighbouring molecule are derived in closed form. These expressions allow one to analyse the physics behind the energy transfer. It is shown that due to different finite lifetimes of the isolated excited molecules, a very efficient vibrational energy transfer can take place between them even if their energies are rather off-resonance. Examples are discussed.