Issue 23, 2024

Identifying a real space measure of charge-shift bonding with probability density analysis

Abstract

Charge-shift bonds have been hypothesized as a third type of chemical bonds in addition to covalent and ionic bonds. They have first been described with valence bond theory where they are identified by the resonance energy resulting from ionic contributions. While other indicators have been described, a clear real space fingerprint for charge-shift bonding is still lacking. Probability density analysis has been developed as a real space method, allowing chemical bonding to be identified from the many-electron probability density |Ψ|2 where the wave function Ψ can be obtained from any quantum chemical method. Recently, barriers of a probability potential, which depends on this density, have proven to be good measures for delocalization and covalent bonding. In this work, we employ many examples to demonstrate that a well-suited measure for charge-shift bonding can be defined within the framework of probability density analysis. This measure correlates well with the charge-shift resonance energy from valence bond theory and thus strongly supports the charge-shift bonding concept. It is, unlike the charge-shift resonance energy, not dependent on a reference state. Moreover, it is independent of the polarity of the bond, suggesting to characterize bonds in molecules by both their polarity and their charge-shift character.

Graphical abstract: Identifying a real space measure of charge-shift bonding with probability density analysis

Supplementary files

Article information

Article type
Edge Article
Submitted
11 Mar 2024
Accepted
06 May 2024
First published
13 May 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 8820-8827

Identifying a real space measure of charge-shift bonding with probability density analysis

M. V. Heinz, L. Reuter and A. Lüchow, Chem. Sci., 2024, 15, 8820 DOI: 10.1039/D4SC01674B

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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