Density functional study of manganese complexes: protonation effects on geometry and magnetism
Density functional study of manganese complexes: protonation effects on geometry and magnetism
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锰配合物的密度泛函研究：质子化对几何和磁性的影响
DOI：
10.1007/978-94-007-5297-9_26
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发表时间：
2012
期刊：
影响因子：
--
通讯作者：
K. Yamaguchi
中科院分区：
文献类型：
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作者：
S. Yamanaka;K. Kanda;T. Saito;Y. Kitagawa;T. Kawakami;M. Ehara;M. Okumura;H. Nakamura;K. Yamaguchi
质子化过程普遍存在于各种生化反应中，如光系统II中的水氧化反应、锰过氧化氢酶和锰超氧化物歧化酶中活性氧物种的解毒等。为了研究它们，探测质子的实验往往需要补充的计算结果来支持实验光谱，而对于实验光谱，需要可靠的密度泛函方法来描述质子化过程。在这项研究中，我们研究了[Mn(IV)2O2Hn(Salpn)2]n+(n=0，1，2)的锰络合物，它们的几何构型和磁性由于质子化而呈现出系统的变化。我们考察了B3LYP、B3LYP-D、BP86、BP86-D和LC-ωPBE在这些变化上的表现。所有的方法都可以再现质子化过程中观察到的变化，定量上最好的程序是LC-ωPBE/LACVP*用于几何优化计算，LC-ωPBE/CHEM用于计算磁相互作用。这一结论有望为含锰蛋白质反应中心的理论研究提供数值基础。
Protonation processes are ubiquitous in various biochemical reactions such as the water-oxidizing reaction in photosystem II and detoxications of active oxygen species in Mn catalase and Mn superoxide dismutase. In order to investigate them, experiments to probe protons often need supplementary computational results to support the experimental spectra, for which reliable DFT methods are required for description of protonation processes. In this study, we investigated manganese complexes, [Mn(IV)2O2Hn(salpn)2]n+(n= 0,1,2), of which geometries and magnetism show systematic changes due to protonations to bridged oxygen anions. We examined the performance of B3LYP, B3LYP-D, BP86, BP86-D, and LC-ωPBE on these changes. With all methods, the observed changes during protonation processes can be reproduced, and the quantitatively best procedure is found to be LC-ωPBE/LACVP* for geometry optimization calculations and LC-ωPBE/chem for calculations of magnetic interactions. This conclusion is expected to be a numerical foundation for theoretical investigation of reaction centers in manganese-containing proteins.