Method of increments for the halogen molecular crystals: Cl, Br, and I
Steenbergen, Krista and Gaston, Nicola and Müller, Carsten and Paulus, Beate – 2014
Method of increments (MI) calculations reveal the n-body correlation contributions to binding in solid chlorine, bromine, and iodine. Secondary binding contributions as well as d-correlation energies are estimated and compared between each solid halogen. We illustrate that binding is entirely determined by two-body correlation effects, which account for >80% of the total correlation energy. One-body, three-body, and exchange contributions are repulsive. Using density-fitting (DF) local coupled-cluster singles, doubles, and perturbative triples for incremental calculations, we obtain excellent agreement with the experimental cohesive energies. MI results from DF local second-order Møller-Plesset perturbation (LMP2) yield considerably over-bound cohesive energies. Comparative calculations with density functional theory and periodic LMP2 method are also shown to be less accurate for the solid halogens.