Convergence of the electrostatic interaction based on topological atoms

Popelier, P.L.A., Joubert, L., and Kosov, D.S. (2001) Convergence of the electrostatic interaction based on topological atoms. Journal of Physical Chemistry: Part A, 105 (35). pp. 8254-8261.

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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.

Item ID: 27290
Item Type: Article (Research - C1)
ISSN: 1520-5215
Date Deposited: 24 Jun 2013 02:59
FoR Codes: 02 PHYSICAL SCIENCES > 0202 Atomic, Molecular, Nuclear, Particle and Plasma Physics > 020201 Atomic and Molecular Physics @ 50%
03 CHEMICAL SCIENCES > 0307 Theoretical and Computational Chemistry > 030701 Quantum Chemistry @ 50%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970102 Expanding Knowledge in the Physical Sciences @ 100%
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