Convergence of the electrostatic interaction based on topological atoms

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

    Research output: Contribution to journalArticlepeer-review


    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°, respecrively) and are both in good to excellent agreement with supermolecule calculations.
    Original languageEnglish
    Pages (from-to)8254-8261
    Number of pages7
    JournalJournal of Physical Chemistry A
    Issue number35
    Publication statusPublished - 6 Sept 2001


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