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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.

Title
Method of increments for the halogen molecular crystals: Cl, Br, and I
Author
Steenbergen, Krista and Gaston, Nicola and Müller, Carsten and Paulus, Beate
Date
2014
Identifier
DOI: 10.1063/1.4896230
Source(s)
Citation
J. Chem. Phys. 2014, 141, 124707