Electrostatics in dissipative particle dynamics using Ewald sums with point charges

TL;DR

This paper develops a method to incorporate electrostatic interactions into dissipative particle dynamics simulations using Ewald sums with point charges, avoiding artificial clustering and accurately predicting polyelectrolyte behavior.

Contribution

It introduces a parameter range for using point charges in DPD with Ewald sums, preventing artificial ion pairing and improving simulation accuracy.

Findings

Larger coarse-graining degrees enable the use of point charges in DPD.

Artificial ionic clustering can be avoided with increased excluded volume interactions.

Predictions of polyelectrolyte scaling agree with other methods and experiments.

Abstract

A proper treatment of electrostatic interactions is crucial for the accurate calculation of forces in computer simulations. Electrostatic interactions are typically modeled using Ewald based methods, which have become one of the cornerstones upon which many other methods for the numerical computation of electrostatic interactions are based. However, their use with charge distributions rather than point charges requires the inclusion of ansatz for the solutions of the Poisson equation, since there is no exact solution known for smeared out charges. The interest for incorporating electrostatic interactions at the scales of length and time that are relevant for the study the physics of soft condensed matter has increased considerably. Using mesoscale simulation techniques, such as dissipative particle dynamics (DPD), allows us to reach longer time scales in numerical simulations, without abandoning the particulate description of the problem. The main problem with incorporating electrostatics into DPD simulations is that DPD particles are soft and those particles with opposite charge can form artificial clusters of ions. Here we show that one can incorporate the electrostatic interactions through Ewald sums with point charges in DPD if larger values of coarse graining degree are used, where DPD is truly mesoscopic. Using point charges with larger excluded volume interactions the artificial formation of ionic pairs with point charges can be avoided, and one obtains correct predictions. We establish ranges of parameters useful for detecting boundaries where artificial formation of ionic pairs occurs. Lastly, using point charges we predict the scaling properties of polyelectrolytes in solvents of varying quality and obtain predictions that are in agreement with calculations that use other methods, and with recent experimental results.