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Maximal orbital analysis of molecular wavefunctions
Journal of Computational Chemistry ( IF 3 ) Pub Date : 2018-09-18 , DOI: 10.1002/jcc.25385
Michel Dupuis 1, 2 , Meghana Nallapu 1
Affiliation  

We describe a new way to decompose one‐electron orbitals of a molecule into atom‐centered or fragment‐centered orbitals by an approach that we call “maximal orbital analysis” (MOA). The MOA analysis is based on the corresponding orbital transformation (COT) that has the unique mathematical property of maximizing any sub‐trace of the overlap matrix, in Hilbert metric sense, between two sets of nonorthogonal orbitals. Here, one set comprises the molecule orbitals (Hartree–Fock, Kohn–Sham, complete‐active‐space, or any set of orthonormal molecular orbitals), the other set comprises the basis functions associated with an atom or a group of atoms. We show in prototypical molecular systems such as a water dimer, metal carbonyl complexes, and a mixed‐valent transition metal complex, that the MOA orbitals capture very well key aspects of wavefunctions and the ensuing chemical concepts that govern electronic interactions in molecules. © 2019 Wiley Periodicals, Inc.

中文翻译:

分子波函数的最大轨道分析

我们描述了一种通过称为“最大轨道分析”(MOA)的方法将分子的单电子轨道分解为原子中心或碎片中心轨道的新方法。MOA 分析基于相应的轨道变换 (COT),该变换具有独特的数学性质,即在希尔伯特度量意义上最大化两组非正交轨道之间的重叠矩阵的任何子迹。在这里,一组包含分子轨道(Hartree-Fock、Kohn-Sham、完全活性空间或任何一组正交分子轨道),另一组包含与一个原子或一组原子相关的基函数。我们展示了原型分子系统,如水二聚体、金属羰基配合物和混合价过渡金属配合物,MOA 轨道很好地捕捉了波函数的关键方面以及随后控制分子中电子相互作用的化学概念。© 2019 威利期刊公司。
更新日期:2018-09-18
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