TY - JOUR
T1 - Asymmetric electrolytes near structured dielectric interfaces
AU - Wu, Huanxin
AU - Li, Honghao
AU - Solis, Francisco
AU - Olvera De La Cruz, Monica
AU - Luijten, Erik
N1 - Publisher Copyright:
© 2018 Author(s).
PY - 2018/10/28
Y1 - 2018/10/28
N2 - The ion distribution of electrolytes near interfaces with dielectric contrast has important consequences for electrochemical processes and many other applications. To date, most studies of such systems have focused on geometrically simple interfaces, for which dielectric effects are analytically solvable or computationally tractable. However, all real surfaces display nontrivial structure at the nanoscale and have, in particular, a nonuniform local curvature. Using a recently developed, highly efficient computational method, we investigate the effect of surface geometry on ion distribution and interface polarization. We consider an asymmetric 2:1 electrolyte bounded by a sinusoidally deformed solid surface. We demonstrate that even when the surface is neutral, the electrolyte acquires a nonuniform ion density profile near the surface. This profile is asymmetric and leads to an effective charging of the surface. We furthermore show that the induced charge is modulated by the local curvature. The effective charge is opposite in sign to the multivalent ions and is larger in concave regions of the surface.
AB - The ion distribution of electrolytes near interfaces with dielectric contrast has important consequences for electrochemical processes and many other applications. To date, most studies of such systems have focused on geometrically simple interfaces, for which dielectric effects are analytically solvable or computationally tractable. However, all real surfaces display nontrivial structure at the nanoscale and have, in particular, a nonuniform local curvature. Using a recently developed, highly efficient computational method, we investigate the effect of surface geometry on ion distribution and interface polarization. We consider an asymmetric 2:1 electrolyte bounded by a sinusoidally deformed solid surface. We demonstrate that even when the surface is neutral, the electrolyte acquires a nonuniform ion density profile near the surface. This profile is asymmetric and leads to an effective charging of the surface. We furthermore show that the induced charge is modulated by the local curvature. The effective charge is opposite in sign to the multivalent ions and is larger in concave regions of the surface.
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U2 - 10.1063/1.5047550
DO - 10.1063/1.5047550
M3 - Article
C2 - 30384706
AN - SCOPUS:85054409648
SN - 0021-9606
VL - 149
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 16
M1 - 164701
ER -