A coherent derivation of the Ewald summation for arbitrary orders of multipoles: The self-terms.

Abstract

In this work, we provide the mathematical elements we think essential for a proper understanding of the calculus of the electrostatic energy of point-multipoles of arbitrary order under periodic boundary conditions. The emphasis is put on the expressions of the so-called self-parts of the Ewald summation where different expressions can be found in the literature. Indeed, such expressions are of prime importance in the context of new generation polarizable force field where the self-field appears in the polarization equations. We provide a general framework, where the idea of the Ewald splitting is applied to the electric potential and, subsequently, all other quantities such as the electric field, the energy, and the forces are derived consistently thereof. Mathematical well-posedness is shown for all these contributions for any order of multipolar distribution.