Theory of chemical bonds in metalloenzymes IV: Hybrid-DFT study of Rieske-type [2Fe-2S] clusters
Theory of chemical bonds in metalloenzymes IV: Hybrid-DFT study of Rieske-type [2Fe-2S] clusters
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DOI：
10.1002/qua.21128
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发表时间：
2007-03-05
影响因子：
2.2
通讯作者：
Yamaguchi, Kizashi
中科院分区：
文献类型：
--
作者：
Shoji, Mitsuo;Koizumi, Kenichi;Yamaguchi, Kizashi
线粒体呼吸链中电子转移 (ET) 蛋白的 Rieske 型 [2Fe-2S] 核心具有不寻常的特性，例如氧化还原电位和光谱学。在本研究（系列的第四部分）中，使用破缺对称杂化密度泛函理论（BS-HDFT）研究了 Rieske 型 [2Fe-2S] 团簇的固有分子结构和特征电子结构。对氧化态和还原态进行了几何优化，并指定了它们的特征振动模式。使用哈密顿量模型研究磁性，以描述电子离域和不对称特性。模型哈密顿量的参数，例如交换耦合 J、价离域 B 和势能差 Delta，通过 BS-HDFT 计算进行评估。讨论了 Rieske 型 [2Fe-2S] 团簇的价态局域化和激发能 (Delta E)。化学键性质通过自然轨道分析的化学指数来表征。我们的理论结果与实验结果相当一致。 (C) 2006 年 Wiley 期刊公司。
The Rieske-type [2Fe-2S] cores of electron-transfer (ET) proteins in the mitochondrial respiratory chain have unusual properties, such as redox potentials and spectroscopy. In this study, part IV of a series, the inherent molecular structures and characteristic electronic structures of the Rieske-type [2Fe-2S] clusters are investigated using broken-symmetry hybrid density functional theory (BS-HDFT). Geometry optimizations for the oxidized and reduced states were performed and their characteristic vibrational modes are assigned. Magnetic properties are investigated using model Hamiltonians to describe the electron delocalization and the unsymmetric property. The parameters of the model Hamiltonian, such as exchange coupling J, valence delocalization B, and potential energy difference Delta, are evaluated from the BS-HDFT calculations. The valence localization and excitation energy (Delta E) of the Rieske-type [2Fe-2S] cluster are discussed. The chemical bond nature is characterized by chemical indices from natural orbital analysis. Our theoretical results are reasonably consistent with experimental results. (C) 2006 Wiley Periodicals, Inc.