Principal interacting orbital: A chemically intuitive method for deciphering bonding interaction,Wiley Interdisciplinary Reviews: Computational Molecular Science

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Principal interacting orbital: A chemically intuitive method for deciphering bonding interaction
Wiley Interdisciplinary Reviews: Computational Molecular Science ( IF 16.8 ) Pub Date : 2020-03-17 , DOI: 10.1002/wcms.1469
Jing-Xuan Zhang ₁ , Fu Kit Sheong ₁ , Zhenyang Lin ₁

Affiliation

Modular bonding picture is a central part of chemical understanding as exemplified by the wide usage of Lewis structure as a chemical language to describe molecular electronic structures. A chemically intuitive bonding picture requires the descriptors to be localized and transferable. Molecular orbitals directly derived from quantum calculations are too delocalized to interpret in this regard, hence many efforts have been devoted to the development of bonding analysis methods. After a brief overview of various bonding analysis methods, this review outlines the framework of principal interacting orbital (PIO) analysis and presents its role in recovering intuitive chemical concepts and producing modular bonding pictures. The PIO analysis identifies the most important fragment orbitals that are involved in fragment interactions and characterizes a one‐to‐one orbital interaction pattern that underlies a unique set of bonding and anti‐bonding orbitals derived from pairwise orbital interactions between two fragments. By making use of the principal component analysis (PCA), PIO analysis can effectively combine complex delocalized interaction patterns involved in numerous molecular orbitals into a handful of localized PIOs to provide easily interpretable results with intimate connection to localized chemical concepts, while maintaining necessary delocalized features when dealing with systems that involve mutlicentered interactions such as cluster compounds and various reactions. Such adaptability guarantees the robustness of PIO analysis with respect to change of substituents and the transferability of obtained PIOs across different systems.

中文翻译：

主要相互作用轨道：化学上直观的键相互作用的破译方法

模块化的键合图是化学理解的核心部分，例如广泛使用Lewis结构作为描述分子电子结构的化学语言的例子。化学上直观的结合图要求描述符是本地化的和可转移的。直接从量子计算得出的分子轨道在此方面太局限了，无法解释，因此，人们为开发键合分析方法付出了很多努力。在简要概述了各种键合分析方法之后，本综述概述了主要相互作用轨道（PIO）分析的框架，并介绍了其在恢复直观化学概念和产生模块化键合图方面的作用。PIO分析确定了片段相互作用中涉及的最重要的片段轨道，并描述了一对一的轨道相互作用模式，该模式是源自两个片段之间成对轨道相互作用的唯一一组键合和反键轨道的基础。通过使用主成分分析（PCA），PIO分析可以有效地将涉及多个分子轨道的复杂的离域相互作用模式组合为少数几个局部PIO，以提供易于解释的结果，并与局部化学概念紧密联系，同时保持必要的离域特征当处理涉及多中心相互作用的系统时，例如簇化合物和各种反应。

更新日期：2020-03-17

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