English

Understanding Radicals via Orbital Parities

Chemical Physics 2024-04-30 v1

Abstract

We introduce analysis of orbital parities as a concept and a tool for understanding radicals. Based on fundamental reduced one- and two-electron density matrices, our approach allows us to evaluate a total measure of radical character and provides spin-like orbitals to visualize real excess spin or odd electron distribution of singlet polyradicals. Finding spin-like orbitals aumotically results in their localization in the case of disjoint (zwitterionic) radicals and so enables radical classification based on spin-site separability. We demonstrate capabilities of the parity analysis by applying it to a number of polyradicals and to prototypical covalent bond breaking.

Keywords

Cite

@article{arxiv.2404.18787,
  title  = {Understanding Radicals via Orbital Parities},
  author = {Reza G. Shirazi and Benedikt M. Schoenauer and Peter Schmitteckert and Michael Marthaler and Vladimir Rybkin},
  journal= {arXiv preprint arXiv:2404.18787},
  year   = {2024}
}
R2 v1 2026-06-28T16:09:56.612Z