Convergence of the multipole expansion for 1,2 Coulomb interactions: The modified multipole shifting algorithm

摘要

A force field that accounts for the quantum chemical reality of interacting atoms must include Coulomb interactions between bonded atoms. The short-range nature of such 1,2 interactions necessitates atomic multipole moments in addition to point charges. However, the close proximity of bonded atoms would normally lead to a divergent multipolar expansion. A special algorithm presented here, within the scope of the previously presented multipole shifting method M. Rafat and P. L. A. Popelier, J. Chem. Phys. 124, 144102 (2006), shows that convergence can nevertheless be achieved by a suitable selection of multipole displacements. The algorithm is applied to improve the convergence of the multipolar expansion within the quantum theory of atoms in molecules approach.