We discuss the formation of weak covalent bonds leading to anionic charge-sharing dimerisation or polymerisation in microscopic cluster environments. The covalent bonding between cluster building blocks is described in terms of coherent charge sharing, conceptualised using a coupled-monomers molecular-orbital model. The model assumes first-order separability of the inter- and intra-monomer bonding structures. Combined with a Hückel-style formalism adapted to weak covalent and solvation interactions, it offers insight into the competition between the two types of forces and illuminates the properties of the inter-monomer orbitals responsible for charge-sharing dimerisation and polymerisation. Under typical conditions, the cumulative effect of solvation obstructs the polymerisation, limiting the size of covalently bound core anions.
|Original language||English (US)|
|Number of pages||15|
|Journal||Physical Chemistry Chemical Physics|
|State||Published - May 28 2021|
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry