Assessment and Validation of the Electrostatically Embedded Many-Body Expansion for Metal-Ligand Bonding.

ABSTRACT

The electrostatically embedded many-body method has been very successful for calculating cohesive energies and relative conformational energies of clusters, and here we extend it to calculate bond breaking energies for metal-ligand bonds in inorganic coordination chemistry. We find that, on average, the electrostatically embedded pairwise additive method is able to predict bond energies yielded by conventional full-system calculations done at the same level of theory to within 2.5 kcal/mol and that the electrostatically embedded three-body method consistently yields energies within 1.0 kcal/mol of the full-system calculations.