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Title: Method of increments for the halogen molecular crystals: Cl, Br, and I

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:
 [1] ;  [2] ;  [3] ; ;  [1]
  1. Physikalische und Theoretische Chemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin (Germany)
  2. (New Zealand)
  3. MacDiarmid Institute for Advanced Materials and Nanotechnology, Victoria University of Wellington, P.O. Box 600, Wellington 6012 (New Zealand)
Publication Date:
OSTI Identifier:
22308244
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 12; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BROMINE; CHLORINE; COMPARATIVE EVALUATIONS; DENSITY; DENSITY FUNCTIONAL METHOD; ELECTRON CORRELATION; IODINE; MOLECULAR CRYSTALS; SOLIDS