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Title: Non-pairwise additivity of the leading-order dispersion energy

The leading-order (i.e., dipole-dipole) dispersion energy is calculated for one-dimensional (1D) and two-dimensional (2D) infinite lattices, and an infinite 1D array of infinitely long lines, of doubly occupied locally harmonic wells. The dispersion energy is decomposed into pairwise and non-pairwise additive components. By varying the force constant and separation of the wells, the non-pairwise additive contribution to the dispersion energy is shown to depend on the overlap of density between neighboring wells. As well separation is increased, the non-pairwise additivity of the dispersion energy decays. The different rates of decay for 1D and 2D lattices of wells is explained in terms of a Jacobian effect that influences the number of nearest neighbors. For an array of infinitely long lines of wells spaced 5 bohrs apart, and an inter-well spacing of 3 bohrs within a line, the non-pairwise additive component of the leading-order dispersion energy is −0.11 kJ mol{sup −1} well{sup −1}, which is 7% of the total. The polarizability of the wells and the density overlap between them are small in comparison to that of the atomic densities that arise from the molecular density partitioning used in post-density-functional theory (DFT) damped dispersion corrections, or DFT-D methods. Therefore, the nonadditivity ofmore » the leading-order dispersion observed here is a conservative estimate of that in molecular clusters.« less
Authors:
 [1]
  1. Department of Chemistry, University of Winnipeg, Winnipeg, Manitoba R3B 2G3, Canada and Department of Chemistry, University of Manitoba, Winnipeg, Manitoba R3T 2N2 (Canada)
Publication Date:
OSTI Identifier:
22416163
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 8; Other Information: (c) 2015 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; ADDITIVES; COMPARATIVE EVALUATIONS; CORRECTIONS; DENSITY; DENSITY FUNCTIONAL METHOD; DIPOLES; MOLECULAR CLUSTERS; ONE-DIMENSIONAL CALCULATIONS; PARTITION; POLARIZABILITY; TWO-DIMENSIONAL CALCULATIONS; TWO-DIMENSIONAL SYSTEMS; WELL SPACING