High-level quantum-chemical calculations, using the coupled-cluster approach and extended one-particle basis sets, have been performed for (${\mathrm{Mg}}^{2+}$${)}_{\mathit{n}}$(${\mathrm{O}}^{2\mathrm{-}}$${)}_{\mathit{m}}$ clusters embedded in a Madelung potential. The results of these calculations are used for setting up an incremental expansion for the correlation energy of bulk MgO. This way approximately 96% of the experimental cohesive energy of the MgO crystal is recovered. It is shown that only about 60% of the correlation contribution to the cohesive energy is of intraionic origin, the remaining part being caused by van der Waals–like interionic excitations.

• Received 2 February 1995

DOI:https://doi.org/10.1103/PhysRevB.52.4842