An extension of Wolf's method for the treatment of electrostatic interactions: application to liquid water and aqueous solutions.

Abstract

We report the results of molecular dynamics simulations, which indicate that, by carefully splitting the electrostatic interactions in short- and long-range contributions and employing the charge-neutralization method of Wolf, accurate predictions of various properties of liquid water and aqueous solutions can be achieved without the need for the Ewald summation. In order to assess the accuracy of the proposed approach, several molecular dynamics simulations under different thermodynamic conditions are performed, employing various rigid, flexible, pairwise additive, and many-body polarizable water models. The predictions of the new approach are compared to the benchmark results obtained with the Ewald summation. It is found that while in the new approach there are no adjustable parameters, such as a damping parameter, the obtained results are more accurate than the results of similar approaches that are based on the Wolf method, while at the same time less or no additional computational effort is required. It is also concluded that the error of the results is smaller or at least comparable to the statistical error of a typical molecular dynamics simulation.