Dynamics of inner- and outer-sphere electron transfer in a polar solvent

In this paper, inner-sphere electron transfer reactions in a solvent are studied in the framework of multidimensional transition state theory. It is demonstrated that the preexponential factor essentially depends upon the interaction with the inner-sphere vibrational mode, increasing the rate of electron transfer as much as one order of magnitude. The prefactor is shown to be strongly dependent on the frequency of this vibration. At high frequencies the rate constant increases with the reorganization energy of this inner-sphere mode while at small frequencies, electron transfer is inhibited. Estimations of inner mode reorganization energies have been performed for system where it is necessary to account nonequilibrium solvent relaxation. Finally it is shown that the equilibrium approximation fails when the reaction is close to an activationless regime.     

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.     

A High-Efficiency Second-Harmonic Gyrotron with a Depressed Collector

The gyrotron with an electrically insulated collector has been manufactured and tested. The 60% output efficiency is obtained for the Collector Potential Depression (CPD) operation regime. The results of the numerical simulation of the electron energy spectrum in the collector region of the second-harmonic technological 24 GHz gyrotron are presented. It is shown, that the minimal electron beam energy is about 20% of the initial value and that the gyrotron cavity should be expanded to achieve the highest output efficiency of the gyrotron with energy recovery. The highest experimental decelerating voltage is in good agreement with the calculation of the electron energy spectrum.     

Theoretical study of the effect of orientation and solvent on energy transfer in bichromophore systems

Results of a quantum-chemical study of the effect of relative orientation of chromophores and solvent on energy transfer in bichromophore systems are presented. The results of theoretical calculations and the experimental data were found to be inconsistent with the prediction of the Förster theory relative to the effect of the orientation factor on the efficiency of energy transfer. It is shown that the effect of solvent on energy transfer is similar to the effect of a connecting bridge in bichromophore molecules. An interpretation of theoretical and experimental results is presented.     

双原子分子内氛重组能的Ab Initio-Morse函数研究

基于重组织现象的自交换模型,提出一种内氛重组能精确的Morse函数标度方案,并对气相电子转移过程中双原子分子体系进行了计算,给出了反应物的结构重组织指标。在HFSCF水平上利用四种基组(6-31G^*、6-31GE、DZ和DZP(d))对标度中所含参数进行了计算,并与实验结果进行比较.结果表明,ab initio计算与实验标度值吻合较好,误差在±1.skcal/mol以内。该方法不仅改进了经典模型而且避免了获得有效的实验数据的困难,给出了一种精确地计算气相电子转移过程中双原子分子内氛重组能的ab initio算法。     

Manifestation of the dynamic properties of the solvent in electron transfer reactions

The ability of the multichannel stochastic model to adequately describe the basic features of the kinetics of thermal electron transfer is demonstrated. It is shown that the solution-controlled regime can be realized in the normal Marcus region, whereas it is almost completely suppressed in the inverted region by the reorganization of high-frequency vibrational modes. The continuous transition between the two regions in the neighborhood of the activationless is quantitatively described. It is found that the dynamic properties of the solvent manifest themselves not only in the dependence of the electron transfer rate on the medium relaxation time τ _L , but also in the free energy gap law, shifting the position of the maximum effective rate constant to higher reaction exergonicities. This shift depends on the longitudinal relaxation time of the medium. In slow solvents, the maximum rate constant of electron transfer can exceed 1/τ _L by several orders of magnitude.     

喇曼自由电子激光器实验的数值模拟

本文采用基于单粒子理论的CAGFEL程序,对中国科学院上海光学精密机械研究所(简称上海光机所)喇曼自由电子激光器的近期实验结果进行了数值模拟,计算表明,当电子能量E_e=0.5MeV,能散度△γ/γ=6％和发射度ξ=0.06(π)rad·cm时,器件的峰值功率高达24MW,对应的辐射增长率为120dB/m,效率为6.1％。     

Electron transfer within 1,3‐dinitrobenzene radical anions: electron hopping or superexchange?

The intramolecular electron transfer on several 1,3‐dinitrobenzene radical anions with different substituents on position 5 was studied by electron paramagnetic resonance and optical spectroscopies in MeCN. The radical anions are all charge‐localized mixed valence species, as is common for meta‐substituted dinitrobenzenes. Rate constants for the electron transfer reaction were obtained by the Marcus–Hush analysis of the intervalence optical bands assuming quartic‐augmented energy surfaces and solvent‐controlled dynamics. These calculated rate constants match quite well the experimental ones obtained by simulation of the electron paramagnetic resonance spectra, which rules out bridge‐reduced states as intermediates in the reaction path and confirms the superexchange mechanism. Copyright © 2012 John Wiley & Sons, Ltd.     

Photoinduced intramolecular electron transfer reactions in fullerene—phenothiazine linked compounds: effects of magnetic field and spacer chain length

Spectroscopic and electrochemical properties of two fullerene(C₆₀)-phenothiazine(PH) linked compounds with different spacer chain length have been compared in benzonitrile (polar solvent) and in benzene (non-polar solvent). Transient absorption and fluorescence spectra indicated that photoinduced intramolecular electron transfer occurred in benzonitrile, but not in benzene. The results are due to solvent effect on energy levels of the photogenerated biradical. The driving forces for the electron transfer were determined by measuring the redox potentials of the C₆₀ and PH moieties. Thermodynamic parameters for the electron transfer processes were evaluated and compared. In benzonitrile, the lifetime of the photo-generated biradical was very long, in spite of being around the top region in Marcus theory. The decay rate of the biradicals was retarded in the presence of magnetic fields. The decay rate constant decreased quickly with increasing the magnetic field and became constant above about 0.2 T. The magnetic field effects verified that the triplet biradical was generated by the intramolecular electron transfer from PH to the triplet excited state of C₆₀. The long lifetime is most probably ascribed to the spin multiplicities of the biradical.     

Frequency dependence of microwave-assisted electron-transfer chemical reactions

In this paper, the electron transfer reactions in the microwave field are studied. A classical theory is developed for a mix of reagents and polar frequency-dispersive and lossy solvent filling vessels excited by microwaves. These reactors are described by a system of non-linear partial self-consistent differential equations for non-stationary microwave field, heat and liquid dynamics, and chemical molecular kinetics. A particular solution of this system is considered for the isothermic electron-transfer reactions in the microwave field varying its frequency with the calculation of the normalised Marcus rate coefficient. It is found that for the small normalised reaction free energy, the chemical reactions are supported by microwaves in a wide frequency band with an increased value of the exponent in the Marcus rate coefficient. At higher values of this energy, these reactions are driven only by conventional microwave heating. The restrictions for the given theory are reviewed, and further experimental and semi-classical and quantum-mechanical studies are found essential for practical applications of these findings.     

丁胺包裹的CdSe量子点敏化的TiO2纳米晶薄膜电子转移机制

利用超快光谱技术系统研究了在丁胺包裹的CdSe量子点敏化的TiO₂纳米晶薄膜起始时刻界面间电子转移动力学。与之前的报道不同,该实验结果表明:CdSe量子点经过表面修饰后,两相电子注入机制--热电子和冷电子注入得以被证实,即:电子能分别从CdSe量子点导带中高的振动能级和导带底转移到TiO₂的导带。该机制详细描绘了电子在纳米界面间转移的图景。进一步研究发现:热电子注入的电子耦合强度(3.6±0.1 meV)比弛豫后的基态电子注入高两个数量级,基于Marcus理论,伴随着0.083 eV的重组能,冷电子注入的耦合强度值为~50 μeV。     

Exact solution for temerature field due to non-equilibrium heating of solid substrate

Non-equilibrium energy transfer between electron and lattice sub-systems due to short-pulse heating is formulated and the closed form solution for electron and lattice site temperatures is presented. The electron kinetic theory approach is incorporated to formulate non-equilibrium energy transfer in the electron and lattice sub-systems. The method of Lie point symmetries is used in the exact solution of governing energy equation. In the analysis, the volumetric heat source, representing the laser heating pulse, and surface heat source, corresponding to short thermal contact of the surface, are incorporated and the analytical solutions for each heating source are presented. Electron temperature distribution obtained from the closed form solution is compared with its counterpart predicted from the numerical simulation. It is found that the results obtained from the closed form agree well with electron temperature predictions obtained from numerical simulation.     

低密度溶液中溶剂的重组织性质

分析了溶液的微观结构 ,结果表明 ,单个溶质粒子影响其周围的溶剂的结构 ,溶质粒子间的相互作用也将影响溶剂的结构 ,溶质对溶剂结构的影响称作溶剂的重组织 .提出了二阶重组织能及二阶重组织熵等概念 ,可以描述在两个溶质粒子发生碰撞时对其周围溶剂结构的影响 .利用二元系的集团展开理论 ,给出了溶剂的一阶、二阶重组织能和重组织熵的表达式 .统计热力学分析给出了溶剂 溶剂径向分布函数与溶质和溶剂化学势之间的关系 ,给出了无限稀溶液模型是否成立的宏观判据 .提出的理论可用于低密度的二元溶液 .     

共面不对称条件下Ar原子(e,2e)反应的三重微分截面

采用修正的扭曲波玻恩近似(DWBA)方法,计算了共面、大能量损失和小动量转移这一特殊几何条件下电子碰撞Ar(3p6)(e,2e)反应的三重微分截面.理论方法对(e,2e)反应过程近程极化势进行了修正,并引入Gamow因子表示后碰撞相互作用(PCI).将计算结果与实验结果、标准DWBA计算结果及Gamow因子修正后的DWBA-G计算结果进行了比较,发现极化效应起着重要的作用.     

上转换对Er3+，Yb3+共掺磷酸盐玻璃激光器输出的影响

研究了激光二极管抽运的Er^３＋，Yb^３＋共掺磷酸盐玻璃激光器中共协上转换(cooperative upconversion)和累积能量转移(cumulative energy transfer)对激光输出的影响.通过对速率方程的数值模拟，定量计算并分析了共协上转换和累积能量转移对激光输出的影响，发现共协上转换对阈值抽运功率的影响可达到22%之多，实验结果和理论曲线相当符合.这有助于对Er^３＋，Yb^３＋共掺磷酸盐玻璃激光器进行优化. 关键词： 共协上转换 累积能量转移 ３＋')" href="#">Er^３＋ ３＋共掺磷酸盐玻璃激光器')" href="#">Yb^３＋共掺磷酸盐玻璃激光器 数值分析     

Influence of the electric field on the electron transport in photosynthetic reaction centers

The effect of an electric field on the electron transfer in the bacterial reaction centers is investigated. The rate constants and quantum yields affected by the electric field for wild type (WT) and reaction center (RC) mutant of Rhodobacter capsulatus were computed. The dependence of the asymmetry of electron transfer in electric field on the temperature was evaluated. We found stable electron transfer for WT of the reaction center towards an electric field in comparison with the F(L121)D mutant of RC. We found quantum yields sensitive to the variation of the medium reorganization energy at low temperatures and strong electric fields. The quantum yields for unoriented RC samples were also calculated.     

量子环中极化子的温度效应

采用求解能量本征方程和LLP幺正变换方法,研究了量子环中极化子的温度效应.数值计算表明:当温度较低时,温度对极化子的基态能量无影响,当温度较高时,极化子的基态能量随温度的升高而增大;还表明极化子的基态能量随电子-声子耦合强度的增大而减小,随电子受限程度的增强(即量子环内径增大或外径减小)而增大,说明其量子尺寸效应非常显著.     

含咔唑取代基喹啉铝衍生物的发光性能：一种潜在的多功能荧光传感材料

研究了一种含咔唑取代基喹啉铝(Alq₃)衍生物的发光性能。首先,研究了溶剂对其发光性能的影响。研究发现,在不同溶剂体系中,Alq₃衍生物在发光过程中均存在不同程度的能量传递;但是,溶剂影响Alq₃衍生物的空间结构和电子结构,进而影响能量传递效率,导致激发光谱、发射光谱、荧光效率和荧光寿命均不相同。其中,甲苯起到能量传递桥梁的作用;而DMF在一定程度上阻碍能量传递。与DMF结构类似的DMA作为电子给体加入到Alq₃衍生物溶液中,也起到了类似作用。另外,研究不同金属离子对Alq₃衍生物发光性能的影响发现,Fe3+和Cu2+可引起Alq₃衍生物的荧光猝灭,表明该Alq₃衍生物可以作为多功能荧光传感材料。     

脉冲管制冷机动态特性数值计算研究

针对脉冲管制冷机内部交变流动及多孔介质蓄冷机的特点建立了数值计算模型,采用改进的数值模拟方法对脉冲管制冷机内部气流的交变流动、换热以及制冷过程进行了详尽的数值研究,得到了脉冲管制冷机内各参数的动态变化,分析了各动态参数变化对制冷机整机性能的影响,并从提高数值方程的计算精度和收敛性方面给出了改进的数值模拟方法。模拟分析与实验结果符合良好。该模拟方法的特点从基本流动换热微分方程出发,尽可能多的考虑实际制冷机工作过程中的各种不可逆因素,包括实际气体的物性变化,各部件的流动阻力和传热损失。     

反射式GaN光电阴极表面势垒对量子效率衰减的影响

针对反射式GaN光电阴极长波段量子效率衰减较大, 短波段量子效率衰减较小的实验现象, 在考虑谷间散射的情况下, 利用玻尓兹曼分布和基于Airy函数的传递矩阵法, 计算了发射电子能量分布, 分析了表面势垒变化对量子效率衰减的影响, 理论与实验符合较好. 激活层有效偶极子数的减少使表面势垒宽度和高度增加, 引起长波光子激发产生的发射电子能量分布衰减较大, 短波光子激发产生的发射电子能量分布衰减较小, 这是量子效率在长波段衰减较大, 短波段衰减较小的根本原因.