The Electronic Structure and Bonding in Some Small Molecules

The electronic structures of the first- and second-row homonuclear diatomics, XeF<sub>2</sub>, and the weakly bound dimers of nitric oxide and nitrogen dioxide molecules in their ground states are discussed in terms of molecular orbital (MO) theory and, where possible, valence bond theor...

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Bibliographic Details
Main Author: George B. Bacskay
Format: Article
Language:English
Published: MDPI AG 2025-03-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/30/5/1154
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Summary:The electronic structures of the first- and second-row homonuclear diatomics, XeF<sub>2</sub>, and the weakly bound dimers of nitric oxide and nitrogen dioxide molecules in their ground states are discussed in terms of molecular orbital (MO) theory and, where possible, valence bond theories. The current work is extended and supported by restricted and unrestricted Hartree–Fock (RHF and UHF) self-consistent field (SCF), complete active space SCF (CASSCF), multi-reference configuration interaction (MRCI), coupled cluster CCSD(T), and unrestricted Kohn–Sham (UKS) density functional calculations using a polarized triple-zeta basis. The dicarbon (C<sub>2</sub>) molecule is especially poorly described by RHF theory, and it is argued that the current MO theories taught in most undergraduate courses should be extended in recognition of the fact that the molecule requires at least a two-configuration treatment.
ISSN:1420-3049