Chemical Bonding and the Role of Node-Induced Electron Confinement

Sterling, Alistair J.; Levine, Daniel S.; Aldossary, Abdulrahman; Head-Gordon, Martin

doi:10.1021/jacs.3c10633

Title: Chemical Bonding and the Role of Node-Induced Electron Confinement

Journal Article · 26 March 2024 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.3c10633 · OSTI ID:2472916

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Univ. of California, Berkeley, CA (United States). Dept. of Chemistry, Kenneth S. Pitzer Center for Theoretical Chemistry; Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States). Dept. of Chemistry, Kenneth S. Pitzer Center for Theoretical Chemistry

The chemical bond is the cornerstone of chemistry, providing a conceptual framework to understand and predict the behavior of molecules in complex systems. However, the fundamental origin of chemical bonding remains controversial and has been responsible for fierce debate over the past century. Here, in this study, we present a unified theory of bonding, using a separation of electron delocalization effects from orbital relaxation to identify three mechanisms [node-induced confinement (typically associated with Pauli repulsion, though more general), orbital contraction, and polarization] that each modulate kinetic energy during bond formation. Through analysis of a series of archetypal bonds, we show that an exquisite balance of energy-lowering delocalizing and localizing effects are dictated simply by atomic electron configurations, nodal structure, and electronegativities. The utility of this unified bonding theory is demonstrated by its application to explain observed trends in bond strengths throughout the periodic table, including main group and transition metal elements.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR). Scientific Discovery through Advanced Computing (SciDAC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2472916

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 14 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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