Model for primary electron transfer and coupling of electronic states at reaction centers of purple bacteria

A detailed derivation is presented for relations making it possible to describe the effect of temperature on the halfwidth of the P960 and P870 absorption bands and also on the electron transfer (ET) rate at reaction centers (RCs) of the purple bacteria Rps. viridis and Rb. sphaeroides. Primary electron transfer is considered as a resonant nonradiative transition between P* and P⁺B _L ⁻ states (where P is a special pair, B_L is an additional bacteriochlorophyll in the L branch of the reaction center). It has been shown that the vibrational h_α mode with frequency 130–150 cm⁻¹ controls primary electron transfer. It has been found that the matrix element of the electronic transition between the states P* and P⁺B _L ⁻ is equal to 12.7 ± 0.9 and 12.0 ± 1.2 cm⁻¹ for Rps. viridis and Rb. sphaeroides respectively. The mechanism is discussed for electron transport from P* and B_L and then to bacteriopheophytin H_L. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 294–303, May–June, 2006.     

光合作用原初过程能量和电荷超快传递过程原理浅析

文章侧重于从物理的角度,介绍光合作用原初过程中能量和电荷超快传递过程的相关物理化学原理,如费米黄金规则,Frster及Dexter传能机制,Marcus电荷转移理论及激子理论.辨析相关原理的适用范围、共性及差异,并力图在上述相关原理的基础上阐述光合膜蛋结构与功能的关系,勾画出该研究方向的基本脉络.     

界面电子转移对量子点荧光闪烁行为的影响

利用激光扫描共聚焦显微系统分别测量了CdSe/ZnS量子点在SiO2玻片表面、铟锡氧化物(ITO)纳米粒子表面和聚甲基丙烯酸甲酯(PMMA)薄膜表面上的荧光闪烁行为.研究发现,不同界面环境中量子点的亮态发光持续时间的概率密度都服从指数修正的幂律分布P(t)∝t-αexp(-t/μ).与处于SiO2玻片表面的情况相比,在ITO表面上的单量子点具有非常短暂的亮态发光持续时间,而在PMMA表面的单量子点亮态发光持续时间最长.这种荧光闪烁行为的不同主要归因于量子点与三种材料之间的界面电子转移特性.     

Evidence for resonance electron transfer in photon excited X-ray satellite spectra of fluorine compounds

The KαL¹/KαL⁰ intensity ratio of fluorine is measured in five fluorine compounds with a crystal spectrometer. An anomalous reduction of this intensity ratio was observed in KF and SrF₂, which is attributed to resonance electron transfer from the metal ion to the spectator vacancy in the fluorine ion. KαL²/KαL⁰ intensity ratio of fluorine is also measured. The measured relative intensities are compared with the theoretical estimates of Aberg. Formerly RSIC     

飞秒激光控制的量子分子动力学研究——多维三能级系统

结合MCTDH方法和优化控制理论，以具有三个电子能级，三个振动自由度的吡嗪分子为例，模拟了优化飞秒激光作用下的量子分子动力学过程. 在对多维两能级系统的优化控制模拟的基础上，以三能级中的两个激发态为目标态，考虑了不同的目标态对多维系统量子动力学过程的影响. 关键词： 飞秒激光控制 MCTDH 方法 量子分子动力学     

The gas phase oxidation of HCOOH by Cl and NH2 radicals. Proton coupled electron transfer versus hydrogen atom transfer*

ABSTRACT

The reaction of formic acid (HCOOH) with chlorine atom and amidogen radical (NH₂) have been investigated using high level theoretical methods such BH&HLYP, MP2, QCISD, and CCSD(T) with the 6–311?+?G(2df,2p), aug-cc-pVTZ, aug-cc-pVQZ and extrapolation to CBS basis sets. The abstraction of the acidic and formyl hydrogen atoms of the acid by the two radicals has been considered, and the different reactions proceed either by a proton coupled electron transfer (pcet) and hydrogen atom transfer (hat) mechanisms. Our calculated rate constant at 298?K for the reaction with Cl is 1.14?×?10^?13?cm³?molecule^?1?s^?1 in good agreement with the experimental value 1.8?±?0.12/2.0?×?10^?13?cm³?molecule^?1?s^?1 and the reaction proceeds exclusively by abstraction of the formyl hydrogen atom, via hat mechanism, producing HOCO+ClH. The calculated rate constant, at 298?K, for the reaction with NH₂ is 1.71?×?10^?15?cm³?molecule^?1?s^?1, and the reaction goes through the abstraction of the acidic hydrogen atom, via a pcet mechanism, leading to the formation of HCOO+NH₃.     

Computational study on intramolecular electron transfer in 1,3‐dintrobenzene radical anion

1,3‐Dinitrobenzene radical anion (DNB^?), which is a typical mixed valence compound, undergoes intramolecular electron transfer (ET) in solution. It is reported that the ET rates exceed 10¹⁰ s^?1 in polar aprotic solvent such as acetonitrile. Formulation based on a simple one‐dimensional model cannot quantitatively account for the observed ET rates, and further study has been desired for better understanding of the solvent effects on the ET. In the present study, molecular dynamics simulations were performed for DNB^? in the vacuum and in acetonitrile solution. In the vacuum, ET was induced by the antisymmetric C–N stretching mode on a timescale of ~100 fs, and the charge transferring between the nitro groups was much less than unity. For the acetonitrile solution, short‐timescale and long‐timescale simulations were performed using a droplet model of solvated DNB^? at 298 K. Although the mean C–N distance in the charged nitro group was longer than that in the vacuum, no ET took place in the short (~150 fs) simulations. The solvent coordinate, which was defined as the difference in the solute–solvent interaction energy between the reactant and the product, significantly fluctuated even in short‐time simulations. The reorganization energies in acetonitrile were evaluated on the basis of molecular orbital (MO) calculations, and the ratio of the inner sphere and outer sphere parts, λ_i/λ_o, was estimated to be ~0.6. The results suggest that the intramolecular mode and fast solvent mode may play an important role in the present ET reaction. Copyright © 2014 John Wiley & Sons, Ltd.     

高电荷态Xe离子与He原子碰撞中的电子转移过程研究

采用位置灵敏探测和飞行时间技术研究了高电荷态Xe离子（q=15，17，19，21，23）与He原子碰撞中双电子转移截面与单电子转移截面比随入射离子电荷态的变化规律.提出一步过程假定，对扩展的经典过垒（ECB）模型进行了修正，利用修正模型计算得到的单、双电子转移绝对截面与Andersson等人和Selberg等人的实验结果很好符合，所得截面比与本实验得到的双电子转移截面与单电子俘获截面比较好符合. 关键词： 离子 原子碰撞 电荷转移 一步过程     

Dynamics of photoinduced electron transfer in model multiporphyrin ensembles

It is shown by the methods of picosecond fluorescent and femtosecond absorptive spectroscopy that in the nanosize self-assembled complexes based on a Zn-octaethylporphyrin dimer and electron acceptors of different nature (quinone, anthraquinone, pyromellitimide) deactivation of the energy of electron excitation is caused by the nonradiative S-S-energy transfer (for times ≤10 psec) and photoinduced charge transfer (within the range of 300 fsec-700 psec). In tetrads an electron is transferred from a porphyrin extra-ligand to quinone for distances r_DA≈18–21 Å by the “superexchange” mechanism. In triads, the charge transfer from a dimer to a fluorinated porphyrin extra-ligand is efficient at 120-77 K.     

The influence of electron intervalley transfer on response pulse width of the MSM photodetector

This paper analyses the influence of nonstationary effects on response pulswidth of Metal-Semiconductor-Metal Photodetector (MSM-PD) made of a two-valley semiconductor. A phenomenological model is used for 2D numerical simulation of carrier transport and intervalley transfer. The analysis of the pulsewidth response of the MSM-PD has been made for various micron and submicron structures, bias voltages and incident light wavelengths.     

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     

低能电子与氮分子碰撞振动激发动量迁移截面的研究

采用作者改进的振动密耦合方法和基于量子力学从头计算的静电势、交换势、相关极化势,研究了低能电子与N₂振动激发散射动量迁移截面. 计算结果与试验符合较好. 关键词： 动量迁移截面 低能电子 分子碰撞 振动激发     

电子在蛋白质分子中的迁移机理及其特性

ATP水解作用所释放的能量能引起蛋白质分子中额外电子的激发,其激发与氨基酸残基晶格畸变相互作用,使额外电子自陷成孤子,这孤子在附着有供体(D)和受体(A)的蛋白质分子中运动时,由于孤子与供体电子的相互作用而"自局域"在孤子上进行迁移,从而可把电子供给受体.使用作者提出的孤子理论研究了这种迁移的特征,计算了在这种非平衡态过程中由孤子迁移电子的速率和动能系数,得到了一些有趣的结果,揭示了这种迁移的本质,求得了迁移的大小.     

A switch in the electron transfer from heme a to binuclear centre of cytochrome c oxidase

New experimental evidence that a switch controls the reduction of the heme a₃－Cu_B binuclear centre has been observed in the N₂-dried thin film of purified cytochrome oxidase. When immersing the enzyme film into the acid phosphate buffer with extremely low concentration of dithionite, a spectrum was given to show a reduction of heme a with no electrons resting on Cu_A. By increasing dithionite, electrons could be accumulated gradually on Cu_A, but the binuclear centre still remains in the oxidized state. When the accumulation of electrons on Cu_A and/or heme a exceeded a threshold, a turnover of reduction of the binuclear centre and oxidation of heme a occurred abruptly. This switch-like action is pH-dependent.     

Structural requirements for efficient photoinduced electron transfer (PET) quenching in 9-aminoalkylanthracenes

The structure-quenching relationship in 9-aminoalkylanthracenes is examined by the synthesis and fluorescence evaluation of five derivatives; it is observed that benzylic 2° and 3° amines lead to 95% quenching of anthracene fluorescence in water, while other amines afford substantially lower quenching efficiencies.     

飞秒电子衍射系统中调制传递函数的理论计算

主要介绍了飞秒电子衍射系统的组成及设计指标. 包括光电阴极、电子聚焦系统、电子偏转系统、双微通道板(MCP)电子探测器等，并给出了基本的设计思路、设计结果. 光电阴极是由位于蓝宝石晶体上面的银膜构成，为了获得足够小的电子束斑以及减小电子上靶时的角度，紧贴栅极后放置一个100μm的小孔，对电子束的形状和大小进行限制. 采用磁电子透镜进行聚焦，电子衍射图样由放置在样品后面的双MCP像增强器进行探测. 在设计计算时，用Monte Carlo方法对光电子的初能量、初角度以及初位置分布进行抽样，用有限元法计算磁透镜 关键词： 飞秒电子枪 有限元法 Monte Carlo模拟 调制传递函数     

调制掺杂GaAs/AlGaAs 2DEG材料持久光电导及子带电子特性研究

在掺Si的GaAs/AlGaAs二维电子气(2DEG)结构中，得到μ_2K=1.78×10^{6cm2/(V·s)的高迁移率.在低温(2K)和高磁场(6T)的条件下，对样品进行红 光辐照，观察到持久光电导(PPC)效应，电子浓度在光照后显著增加.通过整数量子霍尔效应 (IQHE)和Shubnikov-de Haas (SdH)振荡的测量，研究了2DEG的子带电子特性.样品在低温光 照后2DEG中第一子带和第二子带的电子浓度同时随电子总浓度的增加而增加；而且电子迁移 率也明显提高.同时，通过整数霍尔平台的宽度对光照前后电子的量子寿命变短现象作了理 论分析. 关键词： 二维电子气 量子霍尔效应 SdH振荡 持久光电导效应}     

电子在耦合量子阱中振荡的新解法

提供一种新的解法，经过求解微分方程很简单地得到了与殷雯(物理学报52 1862)同样的结果.殷文通过精确求解含时量子体系，研究了在周期耦合驱动下电子在两量子阱中的受迫振荡，不仅得到了一般情况下的振荡公式，而且特别讨论了在ω=0情况下电子布居数的演化行为. 关键词： 耦合量子阱 电子振荡     

Effect of the third component on charge transfer character in ternary organic solar cells with a cascade-type electronic structure

By incorporating a third component into the host donor/acceptor organic components, we theoretically investigate the effects of its electronic structure and spatial location on charge transfer character. It is found that both of the two factors can modulate the distribution of transferred charges, and thus change the role of the third component in charge transfer (i.e., electron donor or acceptor). The binding energy of the formed charge transfer (CT) state is also determined by the two factors. Especially, we find an optimized spatial location of the third component, at which the binding energy of the formed CT state has a minimum value. It suggests that charge separation can be promoted. These findings will provide us a clear direction on how to optimize the electronic structure and spatial location of the third component to further improve the charge transfer and separation in ternary organic solar cells.     

Investigating material trends and lattice relaxation effects for understanding electron transfer phenomena in rare-earth-doped optical materials

Rare-earth-doped insulators and semiconductors play an important role in a wide range of modern optical technologies. Knowledge of the relative energies of rare-earth ions’ localized electronic states and the band states of the host crystal is important for understanding the properties of these materials and for determining the potential material performance in specific applications such as lasers, phosphors, and optical signal processing. Current understanding of the systematic variations of electron binding energies in these materials is reviewed with analysis of how lattice relaxation affects the results obtained from different experimental techniques. Detailed examples are presented for rare-earth-doped YAG and LaF₃ material systems. A method for predicting the chemical shift of the 4f electrons of rare-earth impurities from the host crystal’s photoemission spectrum is also demonstrated. Furthermore, a simple model is presented that predicts host-dependent trends in the binding energies of the rare-earth ion states in materials ranging from the elemental metals to the ionic fluorides. By understanding the systematic changes in the relative energies for different states, different ions, and different host materials, insight is gained into electron transfer transitions, valence stability, and luminescence quenching that can accelerate the development of materials for optical applications.