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

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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.

Bonding situation in MMʹO2 clusters (M, M′ = Be, Mg, Ca)

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Authors and Affiliations

  1. Institute of Chemical Process Fundamentals, Czech Academy of Sciences Prague 6, 165 02, Suchdol 2, Czech Republic

    Robert Ponec

  2. Department of Chemistry, University of Liverpool, Liverpool, L69 7ZD, UK

    David L. Cooper

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  1. Robert Ponec
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  2. David L. Cooper
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Correspondence to Robert Ponec.

Additional information

This paper belongs to Topical Collection International Conference on Systems and Processes in Physics, Chemistry and Biology (ICSPPCB-2018) in honor of Professor Pratim K. Chattaraj on his sixtieth birthday

Electronic supplementary material

Correlation of rMM′ with θMOM′; Dissociation energies from frozen core CCSD(T)/cc-pVQZ; Results using B3LYP calculations; Traditional two-center Wiberg–Mayer indices; Symmetry-unique valence LNOs for each of the clusters; Broken valences resulting from DAFH analysis for the MM′ domain and for one of the O domains in each cluster; Results from a heuristic 3c generalization of Cioslowski’s covalent bond order.

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Ponec, R., Cooper, D.L. Theoretical investigations of the chemical bonding in MM′O2 clusters (M, M′ = Be, Mg, Ca). J Mol Model 24, 226 (2018). https://doi.org/10.1007/s00894-018-3764-y

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