Theory of chemical bonds in metalloenzymes XXII: a concerted bond-switching mechanism for the oxygen–oxygen bond formation coupled with one electron transfer for water oxidation in the oxygen-evolving complex of photosystem II

ABSTRACT

QM(UB3LYP)/MM(AMBER) calculations were performed for the locations of the transition structure (TS) of the oxygen–oxygen (O–O) bond formation in the S₄ state of the oxygen-evolving complex (OEC) of photosystem II (PSII). The natural orbital (NO) analysis of the broken-symmetry (BS) solutions was also performed to elucidate the nature of the chemical bonds at TS on the basis of several chemical indices defined by the occupation numbers of NO. The computational results revealed a concerted bond switching (CBS) mechanism for the oxygen–oxygen bond formation coupled with the one-electron transfer (OET) for water oxidation in OEC of PSII. The orbital interaction between the σ-HOMO of the Mn(IV)₄–O₍₅₎ bond and the π*-LUMO of the Mn(V)₁=O₍₆₎ bond plays an important role for the concerted O–O bond formation for water oxidation in the CaMn₄O₆ cluster of OEC of PSII. One electron transfer (OET) from the π-HOMO of the Mn(V)₁=O₍₆₎ bond to the σ*-LUMO of the Mn(IV)₄–O₍₅₎ bond occurs for the formation of electron transfer diradical, where the generated anion radical [Mn(IV)₄–O₍₅₎]^-? part is relaxed to the ?Mn(III)₄?…?O₍₅₎^- structure and the cation radical [O₍₆₎=Mn(V)₁]⁺ ? part is relaxed to the ⁺O₍₆₎–Mn(IV)₁? structure because of the charge-spin separation for the electron-and hole-doped Mn–oxo bonds. Therefore, the local spins are responsible for the one-electron reductions of Mn(IV)₄->Mn(III)₄ and Mn(V)₁->Mn(IV)₁. On the other hand, the O₍₅₎^- and O₍₆₎⁺ sites generated undergo the O–O bond formation in the CaMn₄O₆ cluster. The Ca(II) ion in the cubane- skeleton of the CaMn₄O₆ cluster assists the above orbital interactions by the lowering of the orbital energy levels of π*-LUMO of Mn(V)₁=O₍₆₎ and σ*-LUMO of Mn(IV)₄–O₍₅₎, indicating an important role of its Lewis acidity. Present CBS mechanism for the O–O bond formation coupled with one electron reductions of the high-valent Mn ions is different from the conventional radical coupling (RC) and acid-base (AB) mechanisms for water oxidation in artificial and native photosynthesis systems. The proton-coupled electron transfer (PC-OET) mechanism for the O–O bond formation is also touched in relation to the CBS-OET mechanism.     

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Research of spatial resolution in external electro-optic probing

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强流束晕-混沌的外部磁场开关控制

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基于光子数目比较的激光测距法

提出了一种新颖的激光测距方法。该方法避开了传统激光测距法中使用复杂辅助电子设备对脉冲计时或比较相位差的过程,而主要通过光学手段分析和提取待测距离信息,最终通过比较大量光子数目的方法求得待测距离。并利用单轴晶体的双折射和全内双反射性质,用特殊结构的单块LiNbO3晶体设计了实施该方法的主体装置。结果表明,该激光测距法同目前普遍使用的激光测距法相比,不但简化了结构,而且有很高的测距精度,从而为激光测距开拓了一种新的思路。     

背景光光伏效应对屏蔽-光伏空间孤子的影响

在光伏晶体两端外加一恒定的直流偏压，背景光的光伏效应对形成屏蔽-光伏孤子的空间电荷场没有影响，但对晶体中的电流有影响.如果外电源的电动势是恒定的，则背景光的光伏效应与外电路的电阻协同起作用，可以通过晶体两端的电压降影响晶体中的空间电荷场，进而影响空间孤子的宽度.在一定的条件下甚至可以实现亮、暗孤子的转换. 关键词： 屏蔽-光伏 空间孤子 孤子宽度 亮暗孤子转换     

光子晶体中四能级系统的量子相干效应

研究了处于光子带隙材料中的四能级原子系统的电磁感应透明、自发辐射和光子开关效应，分析了其稳态与瞬态特性, 发现特殊的模密度能够导致反常的吸收、色散、自发辐射及瞬态无反转增益, 并可以通过外加调制场进行控制.详细讨论了特殊频率处模密度的变化对透明窗口和光子开关效应的影响. 关键词： 光子带隙材料 电磁感应透明 模密度 光子开关     

溶胶-凝胶VO2薄膜转换特性研究

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Polarization inscription in ferroelectric (111) PZT and (100) SBT films

Ferroelectric thin films form an equilibrium domain structure compatible with their respective crystallographic symmetry. In tetragonal (111) PZT, 90° domains prevail; in (pseudo-tetragonal) (100) SBT both 90° and 180° domains are present. The size of 90° domains has been measured for e.g., PZT as slabs of 15 nm width. Domain size is a result of stress minimization in the film during the paraelectric (PE) → ferroelectric (FE) transition. A precise and regular domain pattern for (111) PZT and (100) SBT films has been investigated in detail by TMSFM. Single domains can be addressed mechanically with the tip of an AFM. Such single domain switching corresponds to a data storage density of 200 Gbit/inch². Applications of ferroelectric and high- paraelectric materials for e.g., non-volatile data storage replacing DRAM devices or as sensors in infrared cameras are increasingly becoming popular.