Many-particle covalency, ionicity, and atomicity revisited for a few simple example molecules

We analyze two-particle binding factors of H 2 , LiH, and HeH + molecules/ions with the help of our original exact diagonalization ab initio approach. The interelectronic correlations are taken into account rigorously within the second quantization scheme for restricted basis of renormalized single-...

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Bibliographic Details
Published in:Journal of physics. B, Atomic, molecular, and optical physics Atomic, molecular, and optical physics, 2022-09, Vol.55 (18), p.185101
Main Authors: Hendzel, Maciej, Fidrysiak, Maciej, Spałek, Józef
Format: Article
Language:English
Subjects:
atomicity in molecules
EDABI method
electron correlations
Mottness
resonant covalency
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Summary:We analyze two-particle binding factors of H 2 , LiH, and HeH + molecules/ions with the help of our original exact diagonalization ab initio approach. The interelectronic correlations are taken into account rigorously within the second quantization scheme for restricted basis of renormalized single-particle wave functions, i.e., with their size readjusted in the correlated state. This allows us to determine the many-particle covalency and ionicity factors in a natural and intuitive manner in terms of the microscopic single-particle and interaction parameters, also determined within our method. We discuss the limitations of those basic characteristics and introduce the concept of atomicity, corresponding to the Mott and Hubbard criterion concerning localization threshold in many-particle systems. This addition introduces an atomic ingredient into the electron states and thus removes a spurious behavior of covalency with the increasing interatomic distance, as well as provides a more complete physical interpretation of bonding.
ISSN:0953-4075
1361-6455
DOI:10.1088/1361-6455/ac8298