Principal interacting spin orbital: understanding the fragment interactions in open-shell systems

Abstract

Due to the recent rise in the interest and research efforts on first-row transition metal catalysis and other radical-related reactions, open-shell systems play a much more important role in modern chemistry. However, the development of bonding analysis tools for open-shell systems is still lagging behind. In this work, we present the principal interacting spin orbital (PISO) analysis, which is an analysis framework developed based on our previously reported principal interacting orbital (PIO) analysis. We will demonstrate the power of our framework to analyse different kinds of open-shell systems, ranging from simple organic radicals to much more complicated coordination complexes, from which we can see how different kinds of odd-electron bonds could be identified. We will also illustrate its advantage when used in the analysis of chemical reactions, through which we can observe subtle patterns that could be helpful for tuning or rational design of related reactions.