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A simple method of identifying π orbitals for non-planar systems and a protocol of studying π electronic structure

  • Tian LuEmail author
  • Qinxue Chen
Regular Article
  • 122 Downloads
Part of the following topical collections:
  1. Chemical Concepts from Theory and Computation

Abstract

The characteristic of π electrons has a crucial role in determining various properties of chemical systems, such as reactivity, aromaticity and spectroscopy. There are a large number of methods could be used for investigating π electronic structure, for example, the well-known electron localization function and multicenter bond order. For completely planar systems, the π molecular orbitals can be unambiguously identified and thus studying their π electronic structure is easy. However, for non-planar systems, identification of π orbitals and then analysis of π electrons are often not trivial. In this work, based on localized molecular orbitals (LMOs), we propose a conceptually simple and easy way to automatically identify π orbitals for any kind of systems, which makes subsequent analyses of π electrons straightforward. In addition, we show that the identified π LMOs can also be used to reliably estimate π component of molecular orbitals or other kinds of orbitals. The method proposed in this work has been implemented into our wavefunction analysis code Multiwfn as a key ingredient of standard analysis protocol for π electrons. Application examples given in this article illustrated that this protocol makes analysis of π electronic structure for a wide variety of chemical systems unprecedentedly convenient and reliable.

Keywords

Orbital localization Electron structure Electron localization function Multiwfn Localized orbital locator Electron density π electron Bond order 

Notes

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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2020

Authors and Affiliations

  1. 1.Beijing Kein Research Center for Natural SciencesBeijingPeople’s Republic of China

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