Theoretical investigations of the chemical bonding in MM'O₂ clusters (M, M' = Be, Mg, Ca)

Ponec, Robert and Cooper, David L ORCID: 0000-0003-0639-0794 (2018) Theoretical investigations of the chemical bonding in MM'O₂ clusters (M, M' = Be, Mg, Ca). JOURNAL OF MOLECULAR MODELING, 24 (9). 226-.

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Abstract

Motivated by the known stability of the somewhat unusual Be₂O₂ rhombus, which features a short Be-Be distance but no direct metal-metal bonding, we investigate the nature of the bonding interactions in the analogous clusters MM'O₂ (M, M' = Be, Mg, Ca). CCSD/cc-pVTZ and CCSD(T)/cc-pVQZ calculations, amongst others, are used to determine optimized geometries and the dissociation energies for splitting the MM'O₂ clusters into metal oxide monomers. The primary tools used to investigate the chemical bonding are the analysis of domain-averaged Fermi holes, including the generation of localized natural orbitals, and the calculation of appropriate two- and three-center bond indices. Insights emerging from these various analyses concur with earlier studies of M₂O₂ rhombic clusters in that direct metal-metal bonding was not observed in the MM'O₂ rings whereas weak three-center (3c) bonding was detected in the MOM' moieties. In general terms, these mixed MM'O₂ clusters exhibit features that are intermediate between those of M₂O₂ and M'₂O₂, and the differences between the M and M' atoms appear to have little impact on the overall degree of 3c MOM' bonding. Graphical abstract Bonding situation in MM'O₂ clusters (M, M' = Be, Mg, Ca).

Item Type:	Article
Uncontrolled Keywords:	MM'O-2 rings, Short metal-metal distances without direct bonding, Domain-averaged Fermi hole analysis, Localized natural orbitals, Multicenter bond indices
Depositing User:	Symplectic Admin
Date Deposited:	19 Jul 2018 08:32
Last Modified:	13 Oct 2023 18:13
DOI:	10.1007/s00894-018-3764-y
Related URLs:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3023914