Year: 2025
Type: article
Abstract: ) has been quantum chemically explored using dispersion-corrected relativistic density functional theory (DFT) at ZORA-BLYP-D3(BJ)/TZ2P. We propose a unified picture of chemical bonding that exists on a continuum where weaker van der Waals (commonly referred to as "noncovalent") interactions at longer distances transition into stronger donor-acceptor (commonly referred to as covalent) complexes at shorter distances. Remarkably, depending on the strength of the Lewis base, an intermediate regime is observed where both van der Waals and donor-acceptor complexes are observed. This study demonstrates that a covalent component is ubiquitous across the bonding spectrum, with the stability of the minima on potential energy surfaces determined by the strength of the Lewis acid-base interaction. We advocate for classifying Lewis pairs as strongly or weakly bonded based on whether their covalent interaction is strong enough to overcome the geometric penalty of bond formation. This work elucidates the fuzzy boundaries within chemical bonding.
DOI: 10.1039/d5cp01533b
Authors: Daniela Rodrigues Silva, Lucas de Azevedo Santos, Matthijs A. J. G. Koning, Célia Fonseca Guerra, Trevor A. Hamlin
Institution: Vrije Universiteit Amsterdam
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: hybrid
OpenAlex ID: W4410782819