Dielectric continuum model examination of real-space electrostatic treatments.

Abstract

Electrostatic interaction is long ranged; thus, the accurate calculation is not an easy task in molecular dynamics or Monte Carlo simulations. Though the rigorous Ewald method based on the reciprocal space has been established, real-space treatments have recently become an attractive alternative because of the efficient calculation. However, the construction is not yet completed and is now a challenging subject. In an earlier theoretical study, Neumann and Steinhauser employed the Onsager dielectric continuum model to explain how simple real-space cutoff produces artificial dipolar orientation. In the present study, we employ this continuum model to explore the fundamental properties of the recently developed real-space treatments of three shifting schemes. The result of the distance-dependent Kirkwood function GK(R) showed that the simple bare cutoff produces a well-known hole-shaped artifact, whereas the shift treatments do not. Two-dimensional mapping of electric field well explained how these shift treatments remove the hole-shaped artifact. Still, the shift treatments are not sufficient because they do not produce a flat GK(R) profile unlike ideal no-cutoff treatment. To test the continuum model results, we also performed Monte Carlo simulations of dipolar particles. The results found that the continuum model could predict the qualitative tendency as to whether each electrostatic treatment produces the hole-shaped artifact of GK(R) or not. We expect that the present study using the continuum model offers a stringent criterion to judge whether the primitive electrostatic behavior is correctly described or not, which will be useful for future construction of electrostatic treatments.