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.     

Effect of absorbed pump power on the quality of output beam from monolithic microchip lasers

The dependence of the beam propagation factor (M ² parameter) with the absorbed pump power in the case of monolithic microchip laser under face-cooled configuration is extensively studied. Our investigations show that the M ₂ parameter is related to the absorbed pump power through two parameters (α and β) whose values depend on the laser material properties and laser configuration. We have shown that one parameter arises due to the oscillation of higher order modes in the microchip cavity and the other parameter accounts for the spherical aberration associated with the thermal lens induced by the pump beam. Such dependency of M ² parameter with the absorbed pump power is experimentally verified for a face-cooled monolithic microchip laser based on Nd³⁺ -doped GdVO₄ crystal and the values of α and β parameters were estimated from the experimentally measured data points.     

自聚焦透镜高效批量加工的双面研磨抛光法研究

依据双面研磨抛光原理，提出了加工自聚焦透镜平面和斜面辅助工装设计.从工艺技术特点和生产实际过程等方面对设计的工装使用情况进行分析验证.多次大批量加工实践证明，该辅助工装的设计完全满足了自聚焦透镜高效批量加工技术要求，简化整个生产线工艺，减少工艺流程时间，降低材辅料的消耗成本，从而验证了双面研磨抛光法是一种实用的加工自聚焦透镜的新方法.     

关于左手性介质几何光学的研究（一）

根据几何光学中的费马原理和完善成像原理研究了光线经过正负折射率界面时的传播特性，推导了单负折射率完善成像的曲面方程，讨论了单块负折射率透镜成像特性的一些缺陷及改进方案，依此指出了最短时间原理的适用范围的局限性和利用左手性介质制作光学器件的优越性，为进一步研究左手性介质的光学特性和相关光学器件设计提供了理论基础.     

方形自聚焦透镜的研制

经过方形玻璃丝的加工、离子交换及成品的精密加工等过程，成功制出了方形自聚焦透镜.并采用聚焦成像和雅明干涉等方法对其光学特性进行测试，得出了方形自聚焦透镜本身所具有的一些特性：中心部分畸变较小，成像性能好；四个棱角内的球差较大，像质较差;折射率分布不具有旋转对称性，而是与方向和半径有关.     

光突发交换网络中最长队列优先调度组装机制

提出了光突发交换网络中的最长队列优先调度（LQF-SA）机制，将边缘节点的突发组装和突发调度两种技术紧密结合在一起.在现实网络中，业务通常是非均匀分布的，即在某些源宿对之间存在更大的业务流量.仿真结果表明，LQF-SA机制可以很好地完成非均匀分布业务流的组装.即使在均匀分布业务流输入下，LQF-SA机制在突发大小分布、组装效率和突发丢失率等方面也优于已提出的轮询调度组装（RR-SA）机制.     

多边形棒状透镜出端辐射均匀性的研究

研究了用多角形棒状透镜产生高均匀性正方形和圆形照明的最佳结构参量.结果表明,对于正方形棒状透镜,输出端的照明均匀性随透镜的长度振荡变化,在某些特定长度达到极小值.对于圆形照明面积,比较了从三角到八角的六种多边形.利用三角形积分透镜可以获得最佳的照明均匀性,但光能利用率相对较低,六角形积分透镜可同时获得较高的照明均匀性和光能利用率.     

基于GRIN透镜微小角位移的测量技术研究

根据1/2波节自聚焦（GRIN）透镜中光的传输特性,提出了一种新颖的测量微小角位移的模型,通过对模型中光线传输和几何关系的理论分析,推导了待测角位移与光耦合效率之间的传递函数.针对模型对测量范围的限制,提出了一种可行的拓宽测量范围的方法.研究结果表明,该模型不但测量范围宽,而且测量准确度高,线性度好.     

Changes in the kurtosis parameter of super-Gaussian beams passing through a spherically aberrated lens

Based on the Collins formula and irradiance moments definition, the propagation of the kurtosis parameter of super-Gaussian beams through a spherically aberrated lens is studied. Detailed numerical results are given. It is shown that, as compared with aberration-free super-Gaussian beams, the profile of spherically aberrated super-Gaussian beams can be leptokurtic, mesokurtic or platykurtic, depending on the aberration and propagation distance. The results for the spherically aberrated Gaussian beams can be dealt with as a special case treated in this paper. Finally, the advantage of our method is pointed out.     

光突发交换的交换控制策略和光缓存配置

光突发交换是面向下一代互联网的光交换模式.讨论了异步光突发交换系统的交换控制策略以及相应光缓存的优化配置策略.除了传统预约模式的交换策略,还研究了非预约和改进型预约模式,它们的性能评估由计算机仿真给出.结果表明:在条件相当情况下,改进型预约模式具有最低的丢包率.同时光缓存的配置对上述几类交换控制策略的性能都有很大影响,仿真结果指出:光缓存的粒度对系统性能具有重要影响,所讨论的几类交换模式都存在最佳时延粒度,研究结果对光交换矩阵的设计有指导意义.