The Symmetry-Preserving Mean Field Condition for Electrostatic Correlations in Bulk

Abstract

Accurate simulations of a condensed system of ions or polar molecules are concerned with proper handlings of the involved electrostatics. For such a Coulomb system at a charged planar interface, the Coulomb interaction averaged over the lateral directions with preserved symmetry serves as a necessary constraint in building any accurate handling that reconciles a simulated singlet charge density with the corresponding macroscopic charge/dielectric response. At present, this symmetry-preserving mean-field (SPMF) condition represented in the reciprocal space, is conjectured to be necessary for a simulated bulk system to reproduce correctly the charge structure factor of the macroscopic bulk, as well. In this work, we further examine analytically the asymptotic behavior of the charge structure factor at small wavenumbers for an arbitrary charge-charge interaction. In light of our theoretical predictions, simulations with a length of nearly 0.1 micron are carried out to demonstrate that, typical efficient methods violating the SPMF condition indeed fail to capture the exact charge correlations at small wavenumbers for both ionic and polar systems. However, for both types of systems, these existing methods can be simply amended to match the SPMF condition and subsequently to probe precisely the electrostatic correlations at all length scales.

arXiv comment6 pages, 3 figures

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