期刊
JOURNAL OF CHEMICAL PHYSICS
卷 147, 期 2, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.4986792
关键词
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资金
- China Scholarship Council
- National Science Foundation of China [11104364]
- Chongqing Research Program of Basic Research and Frontier Technology [cstc2015jcyjBX0056]
- Program for Innovation Team Building at Institutions of Higher Education in Chongqing [CXTDX201601030]
- Fluid Interface Reactions, Structures and Transport (FIRST) Center, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences
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. Published by AIP Publishing.
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