Intermolecular Interaction Energies by Topologically Partitioned Electric Properties. I. Electrostatic and Induction Energies in One-Centre and Multi-Centre Multipole Expansions

Georg Jansena, Christof Hättigb, Bernd Artur Heßb, and Janós G. Ángyána,
aLaboratoire de Chemie Théorique, Université de Nancy I, URA CNRS No. 510, B.P. 239, F-54506 Vandoeuvre-lès-Nancy Cedex, France
bInstitut für Physikalische und Theoretische Chemie, Universität Bonn, Wegelerstr. 12, D-53115 Bonn, Germany

Mol. Phys. 88, 69-92 (1996)
(Received 23 October 1995; accepted 30 December 1995)

Certain difficulties with the usual one-centre multipole expansion of long-range intermolecular interaction energies can be circumvented by multi-centre multipole expansions using several expansion sites in each molecule, such as the nuclear positions for example. Based on the topological partitioning of the molecular volume provided by Bader's `Atoms in Molecules' theory we have recently developed a method to calculate the required atomic multipole moments and polarizabilities. We study the performance of these toplogically partitioned electric properties for the calculation of multipole expanded first-order electrostatic and second-order induction energies by comparing their convergence behaviour to that of the corresponding one-centre expansions. The homomolecular dimers of the water, carbon monoxide, cyanogen, and urea molecules serve as examples. The results show that distributed electric properties calculated within the topological partitioning scheme indeed solve the `shape' convergence problem, which arises in the calculation of interaction energies of large non-spherical molecules via multipole expansions.

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