Journal of Molecular Modeling

, 24:226 | Cite as

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

  • Robert Ponec
  • David L. Cooper
Original Paper
Part of the following topical collections:
  1. International Conference on Systems and Processes in Physics, Chemistry and Biology (ICSPPCB-2018) in honor of Professor Pratim K. Chattaraj on his sixtieth birthday


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 MMʹO2 clusters (M, M′ = Be, Mg, Ca)


MM′O2 rings Short metal–metal distances without direct bonding Domain-averaged Fermi hole analysis Localized natural orbitals Multicenter bond indices 

Supplementary material

894_2018_3764_MOESM1_ESM.pdf (1.1 mb)
ESM 1 (PDF 1158 kb)


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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Institute of Chemical Process FundamentalsCzech Academy of Sciences Prague 6Suchdol 2Czech Republic
  2. 2.Department of ChemistryUniversity of LiverpoolLiverpoolUK

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