Ion association at discretely-charged dielectric interfaces: Giant charge inversion [Dielectric response controlled ion association at physically heterogeneous surfaces: Giant charge reversal]

Wang, Zhi -Yong; Wu, Jianzhong

doi:10.1063/1.4986792

Ion association at discretely-charged dielectric interfaces: Giant charge inversion [Dielectric response controlled ion association at physically heterogeneous surfaces: Giant charge reversal]

Journal Article · Tue Jul 11 00:00:00 EDT 2017 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4986792· OSTI ID:1399232

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Chongqing Univ. of Technology, Chongqing (China); Univ. of California, Riverside, CA (United States)
Univ. of California, Riverside, CA (United States)

Giant charge reversal has been identified for the first time by Monte Carlo simulation for a discretely charged surface in contact with a trivalent electrolyte solution. It takes place regardless of the surface charge density under study and the monovalent salt. In stark contrast to earlier predictions based on the 2-dimensional Wigner crystal model to describe strong correlation of counterions at the macroion surface, we find that giant charge reversal reflects an intricate interplay of ionic volume effects, electrostatic correlations, surface charge heterogeneity, and the dielectric response of the confined fluids. While the novel phenomenon is yet to be confirmed with experiment, the simulation results appear in excellent agreement with a wide range of existing observations in the subregime of charge inversion. Lastly, our findings may have far-reaching implications to understanding complex electrochemical phenomena entailing ionic fluids under dielectric confinements.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1399232

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 2 Vol. 147; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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