Revitalizing Spin Natural Orbital Analysis: Electronic Structures of Mixed-Valence Compounds, Singlet Biradicals, and Antiferromagnetically Coupled Systems

J Comput Chem. 2019 Apr 15;40(10):1172-1184. doi: 10.1002/jcc.25762. Epub 2019 Jan 16.

Abstract

Chemical systems with open-shell electronic structure have been gaining attention these days. Their potential applications in first-row transition metal catalysis, molecular wires, photovoltaics and other potential applications have urged the adoption of a simple analysis tool to better understand their open-shell electronic structures, especially the role played by the unpaired electrons. Despite its lack of popularity, spin natural orbital (SNO) analysis is a tool we found to well-suit this purpose. We have therefore re-examined how the SNO could help us analyze some interesting open-shell systems, including mixed-valence compounds, singlet biradicals, and antiferromagnetically coupled systems. We found that some interesting patterns emerge from SNO analysis, especially those associated with exchange interaction. © 2019 Wiley Periodicals, Inc.

Keywords: electronic structure; exchange interaction; open-shell calculation; spin density; spin natural orbital.