Understanding chemistry with the symmetry-decomposed Voronoi deformation density charge analysis

Celine Nieuwland; Pascal Vermeeren; F. Matthias Bickelhaupt; Célia Fonseca Guerra

doi:10.1002/jcc.27184

Understanding chemistry with the symmetry-decomposed Voronoi deformation density charge analysis

Celine Nieuwland, Pascal Vermeeren, F. Matthias Bickelhaupt^*, Célia Fonseca Guerra^*

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

The symmetry-decomposed Voronoi deformation density (VDD) charge analysis is an insightful and robust computational tool to aid the understanding of chemical bonding throughout all fields of chemistry. This method quantifies the atomic charge flow associated with chemical-bond formation and enables decomposition of this charge flow into contributions of (1) orbital interaction types, that is, Pauli repulsive or bonding orbital interactions; (2) per irreducible representation (irrep) of any point-group symmetry of interacting closed-shell molecular fragments; and now also (3) interacting open-shell (i.e., radical) molecular fragments. The symmetry-decomposed VDD charge analysis augments the symmetry-decomposed energy decomposition analysis (EDA) so that the charge flow associated with Pauli repulsion and orbital interactions can be quantified both per atom and per irrep, for example, for σ, π, and δ electrons. This provides detailed insights into fundamental aspects of chemical bonding that are not accessible from EDA.

Original language	English
Pages (from-to)	2108-2119
Number of pages	12
Journal	Journal of Computational Chemistry
Volume	44
Issue number	27
Early online date	5 Jul 2023
DOIs	https://doi.org/10.1002/jcc.27184
Publication status	Published - 15 Oct 2023

Bibliographical note

Funding Information:
The authors thank Dr. Erik van Lenthe for helpful discussions and software implementations, and the Netherlands Organization for Scientific Research (NWO) for financial support. This work was carried out on the Dutch national e‐infrastructure with the support of SURF Cooperative.

Publisher Copyright:
© 2023 The Authors. Journal of Computational Chemistry published by Wiley Periodicals LLC.

Funding

The authors thank Dr. Erik van Lenthe for helpful discussions and software implementations, and the Netherlands Organization for Scientific Research (NWO) for financial support. This work was carried out on the Dutch national e-infrastructure with the support of SURF Cooperative. The authors thank Dr. Erik van Lenthe for helpful discussions and software implementations, and the Netherlands Organization for Scientific Research (NWO) for financial support. This work was carried out on the Dutch national e‐infrastructure with the support of SURF Cooperative.

Funders	Funder number
SURF Cooperative
Nederlandse Organisatie voor Wetenschappelijk Onderzoek

Keywords

atomic charges
bonding analysis
charge analysis
symmetry decomposition
Voronoi deformation density

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10.1002/jcc.27184

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Understanding chemistry with the symmetry-decomposed Voronoi deformation density charge analysis

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Keywords

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