Isotropic periodic sum for multipole interactions and a vector relation for calculation of the Cartesian multipole tensor.

ABSTRACT

Isotropic periodic sum (IPS) is a method to calculate long-range interactions based on the homogeneity of simulation systems. By using the isotropic periodic images of a local region to represent remote structures, long-range interactions become a function of the local conformation. This function is called the IPS potential; it folds long-ranged interactions into a short-ranged potential and can be calculated as efficiently as a cutoff method. It has been demonstrated that the IPS method produces consistent simulation results, including free energies, as the particle mesh Ewald (PME) method. By introducing the multipole homogeneous background approximation, this work derives multipole IPS potentials, abbreviated as IPSMm, with m being the maximum order of multipole interactions. To efficiently calculate the multipole interactions in Cartesian space, we propose a vector relation that calculates a multipole tensor as a dot product of a radial potential vector and a directional vector. Using model systems with charges, dipoles, and/or quadrupoles, with and without polarizability, we demonstrate that multipole interactions of order m can be described accurately with the multipole IPS potential of order 2 or m - 1, whichever is higher. Through simulations with the multipole IPS potentials, we examined energetic, structural, and dynamic properties of the model systems and demonstrated that the multipole IPS potentials produce very similar results as PME with a local region radius (cutoff distance) as small as 6 Å.