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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical study of o-o single bond formation in the oxidation of water by the ruthenium blue dimer
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Theoretical study of o-o single bond formation in the oxidation of water by the ruthenium blue dimer

机译：钌蓝二聚体在水氧化中邻位单键形成的理论研究

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摘要

The first key step in the oxidation of water to O_2 by the oxidized species [(bpy)_2(O)Ru~VORu~V(O)(bpy) _2]~(4+) of the Ru blue dimer is studied using density functional theory (DFT) and an explicit solvent treatment. In the model reaction system [L_2(O)Ru~VORu~V(O)L_2] ~(4+)?(H_2O)_4?W_(76), the surrounding water solvent molecules W are described classically while the inner core reaction system is described quantum mechanically using smaller model ligands (L). The reaction path found for the O-O single bond formation involves a proton relay chain: direct participation of two water molecules in two proton transfers to yield the product [L_2(HOO)Ru~(IV)ORu ~(IV)(OH)L_2]~(4+)?(H_2O) _3?W_(76). The calculated ～3 kcal/mol reaction free energy and ～15 kcal/mol activation free energy barrier at 298 K are consistent with experiment. Structural changes and charge flow along the intrinsic reaction coordinate, the solvent's role in the reaction barrier, and their significance for water oxidation catalysis are examined in detail.
机译：利用密度研究了Ru蓝色二聚体的氧化种[（bpy）_2（O）Ru〜VORu〜V（O）（bpy）_2]〜（4+）将水氧化为O_2的第一步。功能理论（DFT）和显式溶剂处理。在模型反应体系[L_2（O）Ru〜VORu〜V（O）L_2]〜（4 +）？（H_2O）_4？W_（76）中，经典地描述了周围的水溶剂分子W，而内核反应用较小的模型配体（L）来机械地描述量子系统。发现OO单键形成的反应路径涉及质子中继链：两个水分子直接参与两个质子转移以产生产物[L_2（HOO）Ru〜（IV）ORu〜（IV）（OH）L_2] 〜（4 +）？（H_2O）_3？W_（76）。在298 K时计算得到的〜3 kcal / mol反应自由能和〜15 kcal / mol活化自由能垒与实验一致。详细研究了沿固有反应坐标的结构变化和电荷流，溶剂在反应屏障中的作用及其对水氧化催化的意义。

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