电子转移速率理论研究：运动谱窄化所导致的非马尔可夫电子转移过程

严格的速率方程理论得到的总是非马尔可夫的，可是大部分实验都可以用马尔可夫的、即传统的速率常数基础上的反应动力学方程来描述．针对这一问题研究了电子转移过程中的马尔可夫/非马尔可夫特性．以最简单的两态电子转移反应为体系，以其在德拜溶剂中的严格动力学解为标定，采用光谱领域著名的Kubo运动谱窄化线型函数及其特性参数来描述电子转移过程中的马尔可夫/非马尔可夫本质．该马尔可夫特性参数是相干转移耦合与溶剂环境涨落相互影响共同作用的结果，以它为基础说明了大部分实验确实可以通过传统的速率方程来描述，而非马尔可夫速率过程最     

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     

金等离子体中7离子系统(Au47+～Au53+)的电荷态分布及其解析函数关系

根据扩展的相对论多组态Dirac-Fock理论计算得到的Au47 ~Au53 离子的平均离子寿命、能级能量和能级简并度,计算了各离子的电离速率常数、复合速率常数和配分函数,并由此得到了离子间的电离-复合平衡常数.基于这些数据,利用电离复合动力学方法研究了金等离子体内7离子系统在一定电子温度和电子密度下的电荷态分布和平均离化度.并给出了Au47 ~Au53 的离子丰度与电子温度和电子密度的函数关系.     

利用ESR和NMR线宽效应测定二硫蒽及其正离子自由基间的电子交换速率常数

根据ESR和NMR线宽效应,测定了二硫直及其正离子自由基高氯酸盐之间在快交换和慢交换过程中电子转移反应的速率常数.     

芴二聚体三重激发态能量转移的理论研究

利用电子结构计算和电子转移速率理论,研究了芴二聚体的三重激发态能量转移过程. 应用限制性密度泛函理论构造得到非绝热态后,计算了控制能量转移的两个重要参数{电子耦合强度和重组能. 电子耦合强度的波动利用电子动力学模拟计算. 通过对上述参数相关函数的计算,成功得到了体系哈密顿量的对角元和非对角元波动,并应用微扰理论和波包扩散方法得到了能量转移速率. 结果表明,静态和动态的波动都明显地增加了能量转移速率,但是动态波动导致的速度增加却小于静态波动.     

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).     

Nd∶YAG中电声耦合非Markovian过程的激发光谱

用Brown振子模型研究YAG基质材料中Nd^3+ 4f电子跃迁的电子-声子相互作用过程，详尽推导电子．声子耦合的表达式，计算了电声耦合常数不同时的激发光谱，结果表明，电声耦合作用使电子跃迁的吸收峰两边产生声子吸收峰，电声耦合作用较强时，可以产生多级声子吸收峰．通过模拟实验激发光谱，得到样品的电声耦合常数和声子频率等参数，和半导体比较，样品的电声耦合常数较小，说明4f电子．声子的耦合属弱相互作用．用这些参数计算时间分辨的荧光相干光谱，其结果与实验结果一致．     

A1Ⅺ共振电离截面和速率系数

利用改进后的屏蔽常数和Ｚ标度类Ｈ模型理论，计算了电子碰撞Ａ１Ⅺ共振电离截面和速率系数，并把我们计算结果与其他理论结果进行了比较。     

质子碰撞硼原子非辐射的电荷转移过程

重粒子碰撞中的电子转移涉及复杂的电子关联机制,极大地影响等离子体中电荷态平衡,也是X射线的辐射的重要来源之一.电子转移截面与速率系数是国防工业发展核聚变等离子体所需要的重要原子参数.基于全量子的非辐射分子轨道密耦合方法,系统研究了质子碰撞硼原子在10^-3—10³ eV/u能量区间内的硼原子电子转移过程.计算采用多参考组:态方法得到总共15个电子转移、激发以及弹性散射的通道,每个通道对应的分子态能量得到了与实验符合较好的结果.分子态的绝热势能曲线间的避免交叉现象明显,构成了电子转移的主要途径.计算发现,质子碰撞硼原子过程中2s轨道的电子转移是占主导地位,2p轨道的电子转移贡献较小.在低能区,电子转移截面出现了明显的量子共振现象,这些共振主要来源于不同能量通道的耦合.此外,还计算了不同温度下的质子碰撞硼原子的电子转移速率,该速率可为复杂等离子体环境的模拟诊断提供重要的原子参数支持.     

用含时波包方法将SVRT模型应用到F+CD4→CD3+DF反应中

为了实现量子动力学含时波包方法对多原子反应体系的研究,采用美国纽约大学张增辉教授提出的一个半刚性振转子的模型,对F+CD4反应及其同位素反应物反应在MJ1势能面上进行了含时波包动力学的研究.所用到的势能面的反应势垒66meV.实验和理论研究表明在反应中C-D键不影响反应碰撞,它只是一个旁观者.对C-D键作为常数处理使得计算大大简化了.计算了给定初始态的这些反应的积分反应截面和速率常数.从得到的数值结果可以看出,积分截面随着碰撞能有一个很大的起伏,这一般来讲是与动力学振荡有关系.速率常数同已有的理论以及实验结果进行了比较,得到了比较合理的结论.     

Vibrational control of molecular electron transfer reactions

ABSTRACT

Vibrational motions promote molecular electron transfer (ET) reactions by bringing electron donor and electron acceptor electronic states to fleeting resonance, and by modulating the donor-to-acceptor electronic coupling. The main experimental signature of molecular motion effects on the ET rate is the temperature dependence of the rate, which gives information about the overall free energy activation barrier for the ET reaction. Another approach to probing the vibrational control of ET reactions is to excite specific electron-transfer-active vibrational motions by external infrared (IR) fields. This type of experimental probe is potentially more specific than thermal excitation and recent experiments have shown that molecular ET rates can be perturbed by mode-specific IR driving. We review the theory and experiments of vibrational control of ET rates, and discuss future challenges that need to be tackled in order to achieve the mode-specific tuning of rates.     

Electron Transfer Between Molecules: Study with Langevin Equations

In this paper, we investigate the electron transfer （ET） in donor-acceptor model. The Langevin equation with random forces is used. The oscillations of the primary states observed in experimental data have been shown with this approach. And other features on the dependence of the rate of ET on temperature, free energy, and reorganization energy have also been clearly shown.     

On the theory of nonadiabatic bridge-mediated electron transfer

Effects of structural and energetic disorder on nonadiabatic electron transfer (ET) reactions are discussed theoretically. To account for the sequential as well as the superexchange mechanism of ET our recent approach is used presented in J. Phys. Chem. A 105, 10176 (2001). The overall charge motion is characterized by the numerical solution of rate equations for the electronic state populations and an averaging with respect to the disorder configurations. Introducing a single effective transfer rate which can be deduced from the experiment the dependence of this rate is discussed on the geometry of the ET system as well as on the disorder model. The theory is applied to donor-acceptor complexes connected by oligomers of the amino acid proline. In particular, a pronounced dependence is found of the effective transfer rate on disorder with respect to the reorganization energy.Received: 14 April 2003, Published online: 22 July 2003PACS: 34.10.+x General theories and models of atomic and molecular collisions and interactions (including statistical theories, transition state, stochastic and trajectory models, etc.) - 34.30.+h Intramolecular energy transfer; intramolecular dynamics; dynamics of van der Waals molecules - 31.70.Hq Time-dependent phenomena: excitation and relaxation processes, and reaction rates     

Laser pulse control of ultrafast electron transfer reactions

The optimal control (OC) scheme for molecular dynamics is applied to the study of ultrafast bridge mediated electron transfer (ET). Utilizing the methods of dissipative quantum dynamics in combination with the OC approach the guided charge motion in a donor-bridge-acceptor system including a single active vibrational coordinate is studied. The control field drives the optical transition from the electronic ground-state of the ET system into the donor-level and can be used to prepare special electronic and vibrational states. In particular, it is demonstrated that charge localization becomes possible at the acceptor or bridge molecule as well as in the electronic ground-state of the ET system. Received 30 August 2000 and Received in final form 25 October 2000     

Large top-quark mass and nonlinear representation of flavor symmetry

We consider an effective theory (ET) approach to flavor-violating processes beyond the standard model, where the breaking of flavor symmetry is described by spurion fields whose low-energy vacuum expectation values are identified with the standard model Yukawa couplings. Insisting on canonical mass dimensions for the spurion fields, the large top-quark Yukawa coupling also implies a large expectation value for the associated spurion, which breaks part of the flavor symmetry already at the UV scale Lambda of the ET. Below that scale, flavor symmetry in the ET is represented in a nonlinear way by introducing Goldstone modes for the partly broken flavor symmetry and spurion fields transforming under the residual symmetry. As a result, the dominance of certain flavor structures in rare quark decays can be understood in terms of the 1/Lambda expansion in the ET.     

Single molecule electron transfer dynamics in complex environments

We propose a new theoretical approach to study the kinetics of the electron transfer (ET) under the dynamical influence of the complex environments with the first passage times (FPT) of the reaction events. By measuring the mean and high order moments of FPT and their ratios, the full kinetics of ET, especially the dynamical transitions across different temperature zones, is revealed. The potential applications of the current results to single molecule electron transfer are discussed.     

Parametrical study of left-handed or right-handed propagation by stacking hole arrays

In this paper we analyse the recently reported structure with left-handed (LH) propagation obtained by periodically staking subwavelength hole arrays working at the extraordinary transmission (ET) resonance. A parametrical study that clarifies in more detail the equivalent inverse transmission line approach depicted in a previous work is performed. It is seen that ET is necessary to ensure a strong inductive character of the apertures. Additionally, the metal fraction of the unit cell must be large enough in order to favour the electric coupling between plates. What is more, the series capacitance is further increased by setting the plates closer. This allows considering the stacked structure as a metamaterial in that particular dimension. The experimental transmission results previously published are complemented here with a measurement of the reflection coefficient in a stack with LH propagation. These results can give rise to interesting applications such as novel lenses and other quasioptical structures.     

NMR Anomalies in Quasi-2D Organic Superconductors: Effects of Spin Fluctuations in a Fermi Liquid Approach

The -(BEDT-TTF)₂X organic superconductors are described by a two parameter 2D Fermi surface model, in which bandwidth and departure from perfect nesting can be varied. We have studied the spin fluctuations effect on the normal state properties in a Fermi liquid approach using the RPA approximation. The calculated NMR relaxation rate exhibits a peak in 1/(T ₁ T), which strongly decreases when the departure from perfect nesting of the Fermi surface and the bandwidth increase. These results are in good agreement with NMR experiments done in -(ET)₂X at least qualitatively. In conclusion, we have shown that, in the normal state and with a Fermi liquid approach, the spin fluctuations, which are present in the system due to an imperfect nesting property of the Fermi surface, can induce anomalies of the magnetic properties. Besides, we can restore the usual behaviour like the Korringa law by increasing the bandwidth or by considering a more imperfect nesting. Our calculation reproduces qualitatively the applied pressure relaxation rate experiment done in -(ET)₂X salt.     

Scaling analysis of the effects of load on hand tremor movements in essential tremor

In this paper we have used the Wavelet Transform (WT) and the Detrended Fluctuation Analysis (DFA) methods to analyze hand tremor movements in essential tremor (ET), in two different recording conditions (before and after the addition of wrist-cuff load). We have analyzed the time series comprised of peak-to-peak (PtP) intervals, extracted from regions around the first three main frequency components of the power spectra (PwS) of the recorded tremors, in order to substantiate results related to the effects of load on ET, to distinguish between multiple sources of ET, and to separate the influence of peripheral factors on ET.Our results show that, in ET, the dynamical characteristics, that is, values of respective scaling exponents, of the main frequency component of recorded tremors change after the addition of load. Our results also show that in all the observed cases the scaling behavior of the calculated functions changes as well—the calculated WT scalegrams and DFA functions display a shift in the position of the crossover when the load is added. We conclude that the difference in behavior of the WT and DFA functions between different conditions in ET could be associated with the expected pathology in ET, or with some additional mechanism that controls movements in ET patients, and causes the observed changes in scaling behavior.