Convergence of the electrostatic interaction based on topological atoms

Popelier, P.L.A.;Joubert, L.;Kosov, D.S.

Abstract

An atom−atom partitioning of the electrostatic energy between unperturbed molecules is proposed on the basis of the topology of the electron density. Atom−atom contributions to the electrostatic energy are computed exactly, i.e., via a novel six-dimensional integration over two atomic basins, and by means of the spherical tensor multipole expansion, up to total interaction rank L = lA + lB + 1 = 6. The convergence behavior of the topological multipole expansion is compared with that using distributed multipole analysis (DMA) multipole moments for a set of van der Waals complexes at the B3LYP/6-311+G(2d,p) level. Within the context of the Buckingham−Fowler model it is shown that the topological and DMA multipole moments converge to a very similar interaction energy and geometry (average absolute discrepancy of 1.3 kJ/mol and 1.3°, respectively) and are both in good to excellent agreement with supermolecule calculations.

Journal

Journal of Physical Chemistry: Part A

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105

ISBN/ISSN

1520-5215

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Publisher

American Chemical Society

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DOI

10.1021/jp011511q