Ion association at discretely-charged dielectric interfaces: Giant charge inversion [Dielectric response controlled ion association at physically heterogeneous surfaces: Giant charge reversal]
- 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.
- Research Organization:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Grant/Contract Number:
- AC05-00OR22725
- OSTI ID:
- 1399232
- Journal Information:
- Journal of Chemical Physics, Vol. 147, Issue 2; ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
Web of Science
On the physics of both surface overcharging and charge reversal at heterophase interfaces
|
journal | January 2018 |
Simulations of Coulomb systems confined by polarizable surfaces using periodic Green functions
|
journal | November 2017 |
Similar Records
Effective interactions between rigid polyelectrolytes and like-charged planar surfaces
Reversible Adhesion with Polyelectrolyte Brushes Tailored via the Uptake and Release of Trivalent Lanthanum Ions