Accurate Dissociation of Chemical Bonds Using DFT-in-DFT Embedding Theory with External Orbital Orthogonality.
Accurate Dissociation of Chemical Bonds Using DFT-in-DFT Embedding Theory with External Orbital Orthogonality.
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使用具有外轨道正交性的 DFT-in-DFT 嵌入理论精确解离化学键。
DOI：
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发表时间：
2017
影响因子：
2.9
通讯作者：
M. Hoffmann
中科院分区：
文献类型：
--
作者：
Patrick K. Tamukong;Y. Khait;M. Hoffmann
我们最近的密度泛函理论（DFT）中的DFT嵌入协议，强制子系统间（或外部轨道）正交，是第一次用来研究共价键解离，并证明这样做是准确的。使用新的嵌入方法构建了H2O中H-O键和H3C-CH 3中C-C键解离的全势能曲线，以及LiH和LiF中具有挑战性的离子键，并发现与参考Kohn-Sham（KS）-DFT曲线至少有一部分匹配。增加的外部轨道正交性的约束，允许制定的嵌入协议，不依赖于近似动能泛函的所谓的非加性动能潜力的评估，不引入补偿潜力，并不需要在任何阶段的总系统计算。目前的工作扩展了嵌入理论的外部正交性变体的证明适用性的强单键的相互作用强度范围的2倍以上。特别是，它表明，均裂成自由基的共价键和离子键可以完成。
Our recent density functional theory (DFT)-in-DFT embedding protocol, which enforces intersubsystem (or external orbital) orthogonality, is used for the first time to investigate covalent bond dissociation and is shown to do so accurately. Full potential energy curves for the dissociation of a H-O bond in H2O and the C-C bond in H3C-CH3 have been constructed using the new embedding method, as have the challenging ionic bonds in LiH and LiF, and were found to match the reference Kohn-Sham (KS)-DFT curves to at least one part in 106. The added constraint of external orbital orthogonality allows for the formulation of an embedding protocol that does not rely on approximate kinetic energy functionals for the evaluation of the so-called nonadditive kinetic potential, does not introduce compensatory potentials, and does not require a total system calculation at any stage. The present work extends the demonstrated applicability of the external orthogonality variant of embedding theory by more than a factor of 2 to the interaction strength range of strong single bonds. In particular, it is demonstrated that homolytic cleavage of both covalent and ionic bonds into radicals can be accomplished.
DOI：
10.1021/jp902710a
发表时间：
2009-10-29
期刊：
The journal of physical chemistry. A
影响因子：
--
作者：
Song L;Han J;Lin YL;Xie W;Gao J
通讯作者：
Gao J
相关波函数的密度泛函理论嵌入：开壳系统和过渡金属配合物的改进方法。
DOI：
10.1063/1.4770226
发表时间：
2012
期刊：
The Journal of chemical physics
影响因子：
--
作者：
Goodpaster JD
通讯作者：
Goodpaster JD