EHF theory of chemical reactions V. Nature of manganese–oxygen bonds by hybrid density functional theory (DFT) and coupled‐cluster (CC) methods
EHF theory of chemical reactions V. Nature of manganese–oxygen bonds by hybrid density functional theory (DFT) and coupled‐cluster (CC) methods
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化学反应的 EHF 理论 V. 通过混合密度泛函理论 (DFT) 和耦合簇 (CC) 方法研究锰-氧键的性质
DOI：
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发表时间：
2001
期刊：
影响因子：
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通讯作者：
K. Yamaguchi
中科院分区：
文献类型：
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作者：
H. Isobe;Tomohisa Soda;Y. Kitagawa;Y. Takano;T. Kawakami;Y. Yoshioka;K. Yamaguchi
通过描述氢过氧化物的O-O解离和过渡金属氧化物的M-O解离的势能曲线，比较了杂化密度泛函理论（DFT）和post-Hartree-Fock方法.前一种方法包括BLYP、B2 LYP、B3 LYP和更一般的混合DFT方法，而非限制性Hartree-Fock（UHF）耦合簇（UCC）SD（T）方法被认为是后一种方法。混合密度泛函方法可以再现O-O解离过程的势能曲线和由UCCSD（T）计算的HOOH解离能。该方法也适用于描绘氧化铜（CuO）和氧化锰（MnO）的电势曲线，并重现实验M-O结合能。本文研究了裸Mn-O、Mn-O卟啉体系和模型配合物XH_3Mn（IV）O_2Mn（IV）H_3Y（X，Y=O，H）中Mn-O键的性质与氧化反应的可能机理。结果表明，随着Mn离子氧化数的增加，Mn-O键的自由基性质增强。John Wiley & Sons，Inc.国际量子化学杂志，2001年
Hybrid density functional theory (DFT) and post-Hartree–Fock methods are compared by depicting potential energy curves of the O–O dissociation of hydroperoxide and the M–O dissociation of transition-metal oxides. The former approach includes BLYP, B2LYP, B3LYP, and more general hybrid DFT methods, while the unrestricted Hartree–Fock (UHF) coulpled-cluster (UCC) SD(T) method is considered as the latter approach. The hybrid DFT methods can reproduce the potential curve of the O–O dissociation process and the dissociation energy of HOOH by UCCSD(T). The methods are also useful for depicting potential curves of copper oxide (CuO) and manganese oxide (MnO), and reproduce the experimental M–O binding energies. The nature of Mn–O bonds in the naked Mn–O, Mn–O porphyrine system and model complexes, XH3Mn(IV)O2Mn(IV)H3Y (X,Y=O,H), are examined in relation to the possible mechanisms of oxygenation reactions. It is found that the radical character of Mn–O bonds increases with the increase of the oxidation number of the Mn ion in these systems. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001
影响因子：
56.9
作者：
Limburg, J;Vrettos, JS;Brudvig, GW
通讯作者：
Brudvig, GW