title: Method of increments for the halogen molecular crystals: Cl, Br, and I.
abstract: 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.
authors.affiliation: Physikalische und Theoretische Chemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany.
authors.forename: Krista G
authors.initials: KG
authors.lastname: Steenbergen
authors.affiliation: MacDiarmid Institute for Advanced Materials and Nanotechnology, Victoria University of Wellington, P.O. Box 600, Wellington 6012, New Zealand.
authors.forename: Nicola
authors.initials: N
authors.lastname: Gaston
authors.affiliation: Physikalische und Theoretische Chemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany.
authors.forename: Carsten
authors.initials: C
authors.lastname: Müller
authors.affiliation: Physikalische und Theoretische Chemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany.
authors.forename: Beate
authors.initials: B
authors.lastname: Paulus