TY - JOUR
T1 - Pimples reduce and dimples enhance flat dielectric surface image repulsion
AU - Solis, Francisco J.
AU - Olvera de la Cruz, Monica
N1 - Funding Information:
We thank Dr. Trung Nguyen for assistance in the preparation of the comparison between analytical and numerical results in Fig. 4. We acknowledge the NSF (Grant No. DMR-1611076) for support during the time this project was initiated. The authors have no conflicts to disclose.
Publisher Copyright:
© 2021 Author(s).
PY - 2021/9/14
Y1 - 2021/9/14
N2 - In solid-liquid, or liquid-liquid, interfaces with dielectric contrast, charged particles interact with the induced polarization charge of the interface. These interactions contribute to an effective self-energy of the bulk ions and mediate ion-ion interactions. For flat interfaces, the self-energy and the mediated interactions are neatly constructed by the image charge method. For other geometries, explicit results are scarce and the problem must be treated via approximations or direct computation. The case of interfaces with roughness is of great practical importance. This article provides analytical results, valid to first-order in perturbation theory, for the self-energy of particles near rough substrates. Explicit formulas are provided for the case of a sinusoidal deformation of a flat surface. Generic deformations can be treated by superposition. In addition to results for the self-energy, the surface polarization charge is presented as a quadrature. The interaction between an ion and the deformed surface is modified by the change in relative distance as well as by the local curvature of the surface. Solid walls, with a lower dielectric constant than the liquid, repel all ions. We show that the repulsion is reduced by local convexity and enhanced by concavity; dimples are more repulsive than pimples.
AB - In solid-liquid, or liquid-liquid, interfaces with dielectric contrast, charged particles interact with the induced polarization charge of the interface. These interactions contribute to an effective self-energy of the bulk ions and mediate ion-ion interactions. For flat interfaces, the self-energy and the mediated interactions are neatly constructed by the image charge method. For other geometries, explicit results are scarce and the problem must be treated via approximations or direct computation. The case of interfaces with roughness is of great practical importance. This article provides analytical results, valid to first-order in perturbation theory, for the self-energy of particles near rough substrates. Explicit formulas are provided for the case of a sinusoidal deformation of a flat surface. Generic deformations can be treated by superposition. In addition to results for the self-energy, the surface polarization charge is presented as a quadrature. The interaction between an ion and the deformed surface is modified by the change in relative distance as well as by the local curvature of the surface. Solid walls, with a lower dielectric constant than the liquid, repel all ions. We show that the repulsion is reduced by local convexity and enhanced by concavity; dimples are more repulsive than pimples.
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U2 - 10.1063/5.0058810
DO - 10.1063/5.0058810
M3 - Article
C2 - 34525828
AN - SCOPUS:85115130750
SN - 0021-9606
VL - 155
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 10
M1 - 104703
ER -