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J Chem Phys ; 132(13): 134303, 2010 Apr 07.
Artículo en Inglés | MEDLINE | ID: mdl-20387929

RESUMEN

Localized molecular orbital energy decomposition analysis and symmetry-adapted perturbation theory (SAPT) calculations are used to analyze the two- and three-body interaction energies of four low-energy isomers of (H(2)O)(6) in order to gain insight into the performance of several popular density functionals for describing the electrostatic, exchange-repulsion, induction, and short-range dispersion interactions between water molecules. The energy decomposition analyses indicate that all density functionals considered significantly overestimate the contributions of charge transfer to the interaction energies. Moreover, in contrast to some studies that state that density functional theory (DFT) does not include dispersion interactions, we adopt a broader definition and conclude that for (H(2)O)(6) the short-range dispersion interactions recovered in the DFT calculations account about 75% or more of the net (short-range plus long-range) dispersion energies obtained from the SAPT calculations.

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