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. Our findings may have far-reaching implications to understanding complex electrochemical phenomena entailing ionic fluids under dielectric confinements.
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Ion association at discretely-charged dielectric interfaces: Giant charge inversion
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14 July 2017
Research Article|
July 11 2017
Ion association at discretely-charged dielectric interfaces: Giant charge inversion
Zhi-Yong Wang
;
Zhi-Yong Wang
a)
1
School of Science, Chongqing University of Technology
, Chongqing 400054, China
2
Department of Chemical and Environmental Engineering, University of California
, Riverside, California 92521, USA
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Jianzhong Wu
Jianzhong Wu
b)
2
Department of Chemical and Environmental Engineering, University of California
, Riverside, California 92521, USA
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J. Chem. Phys. 147, 024703 (2017)
Article history
Received:
May 01 2017
Accepted:
June 02 2017
Citation
Zhi-Yong Wang, Jianzhong Wu; Ion association at discretely-charged dielectric interfaces: Giant charge inversion. J. Chem. Phys. 14 July 2017; 147 (2): 024703. https://doi.org/10.1063/1.4986792
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