An exact method to obtain effective electrostatic interactions from computer simulations: The case of effective charge amplification

P. González-Mozuelos, G. I. Guerrero-García, M. Olvera De La Cruz*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

20 Scopus citations

Abstract

We discuss here an exact method to determine the parameters regulating the screened Coulomb interactions among spherical macroions immersed in a simple electrolyte. This approach provides rigorous definitions for the corresponding screening length, effective permittivity, and renormalized charges, and can be employed for precise and reliable calculations of these parameters within any scheme. In particular, we introduce a simple procedure for extracting this information from computer simulations. The viability of this approach is demonstrated by applying it to a three-component model system which includes anionic nanoparticles and monovalent cations and anions. The mean forces between nanoparticles are determined directly from simulations with two macroions, plus small ions, inside a single cell with periodic boundary conditions. The values of the parameters of interest, on the other hand, are gathered from two separate sets of computer simulations: one set provides information about the short-range correlations among the small ions, which in turn determine the screening length and effective permittivity; the second set supplies the short-range components of the ionic distribution around one isolated macroion, which also determine its renormalized charge. The method presented here thus avoids the uncertain fitting of these parameters from the asymptotic tail of the mean force and allows us to investigate in detail this connection between the renormalized charge of the macroion and the short-range (virtual) part of the ionic cloud surrounding it. Using the standard prescription to extract an effective charge from the corresponding renormalized value, we then proceed to clarify the mechanisms behind the possibility of effective charge amplification (i.e., an effective charge larger than the bare macroion charge). Complementarily, we report results for the corresponding bridge functions too.

Original languageEnglish (US)
Article number064709
JournalJournal of Chemical Physics
Volume139
Issue number6
DOIs
StatePublished - Aug 14 2013

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Fingerprint Dive into the research topics of 'An exact method to obtain effective electrostatic interactions from computer simulations: The case of effective charge amplification'. Together they form a unique fingerprint.

Cite this