Bond formation insights into the Diels-Alder reaction: A bond perception and self-interaction perspective

TL;DR

This paper introduces computationally derived bond descriptors from localized orbitals and self-interaction corrections to automatically analyze bond formation in the Diels-Alder reaction, providing a clear electronic perspective.

Contribution

It presents a novel method for automatic bond perception using intrinsic descriptors from advanced quantum chemistry calculations, enhancing understanding of the Diels-Alder reaction.

Findings

Descriptors visualize concerted bond formation and breaking.

Descriptors align with Lewis' bonding theory.

Method enables educational and electronic inspection of reactions.

Abstract

The behavior of electrons during bond formation and breaking cannot commonly be accessed from experiments. Thus, bond perception is often based on chemical intuition or rule-based algorithms. Utilizing computational chemistry methods, we present intrinsic bond descriptors for the Diels-Alder reaction, allowing for an automatic bond perception. We show that these bond descriptors are available from localized orbitals and self-interaction correction calculations, e.g., from Fermi-orbital descriptors. The proposed descriptors allow a sparse, simple, and educational inspection of the Diels-Alder reaction from an electronic perspective. We demonstrate that bond descriptors deliver a simple visual representation of the concerted bond formation and bond breaking, which agrees with Lewis' theory of bonding.