Correlation effects in ionic crystals: I. The cohesive energy of MgO

TL;DR

This paper uses high-level quantum-chemical calculations to accurately estimate the cohesive energy of MgO, revealing the significant role of inter-ionic excitations beyond intra-ionic correlations.

Contribution

It introduces an incremental expansion method based on quantum-chemical calculations to estimate bulk MgO cohesive energy, capturing 96% of the experimental value.

Findings

96% of experimental cohesive energy recovered

60% of correlation energy is intra-ionic

Inter-ionic excitations significantly contribute to cohesion

Abstract

High-level quantum-chemical calculations, using the coupled-cluster approach and extended one-particle basis sets, have been performed for (Mg2+)n (O2-)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, 96% of the experimental cohesive energy of the MgO crystal is recovered. It is shown that only 60% of the correlation contribution to the cohesive energy is of intra-ionic origin, the remaining part being caused by van der Waals-like inter-ionic excitations.