Abstract
Motivated by the particularly short metal-metal distance that has been predicted for the D3h [BeH3Be]+ cation, comparable to those anticipated for triple bonds, we investigate the nature of the bonding interactions in the D3h [MH3M]+ cations (M = Be, Mg). CCSD(T)/cc-pVQZ calculations are used to determine optimized geometries for all of the various species, including those “capped” by He or Ne atoms (as proxies for an inert gas matrix). The primary tools that are then used to investigate the nature of the chemical bonding are spin-coupled generalized valence bond calculations and the analysis of localized natural orbitals and of domain-averaged Fermi holes. The various results for all of the systems considered indicate the presence of highly polar three-center two-electron M─H─M bonding character instead of any significant direct metal-metal bonding.
| Original language | English |
|---|---|
| Article number | e26183 |
| Number of pages | 7 |
| Journal | INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY |
| Early online date | 8 Feb 2020 |
| DOIs | |
| Publication status | Published - 20 Apr 2020 |
Bibliographical note
© 2020 Wiley Periodicals, Inc. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.Keywords
- domain-averaged Fermi hole analysis
- localized natural orbitals
- spin-coupled generalized valence bond (SCGVB) calculations
- three-center two-electron bonding
- ultrashort metal-metal distances