Distributed multipoles from a robust basis-space implementation of the iterated stockholder atoms procedure

Abstract

The recently developed iterated stockholder atoms (ISA) approach of Lillestolen and Wheatley (Chem. Commun. {\bf 2008}, 5909 (2008)) offers a powerful method for defining atoms in a molecule. However, the real-space algorithm is known to converge very slowly, if at all. Here we present a robust, basis-space algorithm of the ISA method and demonstrate its applicability on a variety of systems. We show that this algorithm exhibits rapid convergence (taking around 10--80 iterations) with the number of iterations needed being unrelated to the system size or basis set used. Further, we show that the multipole moments calculated using this basis-space ISA method are as good as, or better than those obtained from Stone's distributed multipole analysis (J. Chem. Theory Comput. {\bf 1}, 1128 (2005) ), exhibiting better convergence properties and resulting in better behaved penetration energies. This can have significant consequences in the development of intermolecular interaction models.