A New Relatively Simple Approach to Multipole Interactions in Either Spherical Harmonics or Cartesians, Suitable for Implementation into Ewald Sums

Abstract

We present a novel derivation of the multipole interaction (energies, forces and fields) in spherical harmonics, which results in an expression that is able to exactly reproduce the results of earlier Cartesian formulations. Our method follows the derivations of Smith (W. Smith, CCP5 Newsletter 1998, 46, 18.) and Lin (D. Lin, J. Chem. Phys. 2015, 143, 114115), who evaluate the Ewald sum for multipoles in Cartesian form, and then shows how the resulting expressions can be converted into spherical harmonics, where the conversion is performed by establishing a relation between an inner product on the space of symmetric traceless Cartesian tensors, and an inner product on the space of harmonic polynomials on the unit sphere. We also introduce a diagrammatic method for keeping track of the terms in the multipole interaction expression, such that the total electrostatic energy can be viewed as a ‘sum over diagrams’, and where the conversion to spherical harmonics is represented by ‘braiding’ subsets of Cartesian components together. For multipoles of maximum rank n, our algorithm is found to have scaling of n 3.7 vs. n 4.5 for our most optimised Cartesian implementation.