Computational Characterization of Single-Electron Transfer Steps in Water Oxidation
Computational Characterization of Single-Electron Transfer Steps in Water Oxidation
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DOI：
10.3390/inorganics7030032
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发表时间：
2019-03-01
期刊：
影响因子：
2.9
通讯作者：
Maseras, Feliu
中科院分区：
文献类型：
--
作者：
de Aguirre, Adiran;Funes-Ardoiz, Ignacio;Maseras, Feliu
第一行过渡金属配合物催化水氧化过程中的单电子转移（SET）步骤的存在最近已被确认，但这种类型的过程的计算表征是不平凡的。我们报告了一个系统的理论研究的基础上，密度泛函理论（DFT）计算的一个特定的铜配合物的活性在水的氧化，通过两个连续的单电子转移反应的反应。内球（通过过渡态位置）和外球（通过马库斯理论）机制进行了分析。第一次电子转移是通过外球进行的，第二次是通过内球进行的。本工作为水氧化催化及其他领域的单电子转移的系统研究提供了一个方案。
The presence of single-electron transfer (SET) steps in water oxidation processes catalyzed by first-row transition metal complexes has been recently recognized, but the computational characterization of this type of process is not trivial. We report a systematic theoretical study based on density functional theory (DFT) calculations on the reactivity of a specific copper complex active in water oxidation that reacts through two consecutive single-electron transfers. Both inner-sphere (through transition state location) and outer-sphere (through Marcus theory) mechanisms are analyzed. The first electron transfer is found to operate through outer-sphere, and the second one through inner-sphere. The current work proposes a scheme for the systematic study of single-electron transfer in water oxidation catalysis and beyond.