Improved convergence of the ‘atoms in molecules’ multipole expansion of electrostatic interaction

Abstract

We study the anisotropic electrostatic interaction with high rank multipoles (ℓ = 5) for a set of 10 van der Waals complexes and 27 DNA base pairs. Multipoles are generated by the distributed multipole analysis (DMA) and by the topological quantum theory of ‘atoms in molecules’ (AIM). The convergence of the multipolar expansion of the interaction between topological atoms is improved by distributing the moments over extra off-nuclear sites via a shifting procedure. A clear theoretical distinction is made between partitioning and distributing. A substantial improvement in the convergence of the AIM multipole expansion is observed for the smaller van der Waals molecules. An AIM representation with extra sites on the bond midpoints performs as well as DMA with just nuclear sites. However, for the larger DNA base pairs no improvement follows from the introduction of extra sites with AIM. For these larger systems AIM and DMA expansions perform equivalently, provided that now DMA allows for extra sites. This work further encourages the development of a topological intermolecular force field.