2014/09/09 by Ali Naji, Malihe Ghodrat, Haniyeh Komaie-Moghaddam +1 · 1 citation
Chemistry · Earth and Planetary Sciences · Physics and Astronomy · #Charge (physics) #Chemical physics #Condensed matter physics #Coulomb #Dielectric #Electron #Electrostatics and Colloid Interactions #Fragility #Geology #Geophysical and Geoelectrical Methods #Inversion (geology) #Materials science #Optoelectronics #Physics #Quantum mechanics #Seismology #Surface and Thin Film Phenomena #Thermodynamics #cond-mat.dis-nn #cond-mat.soft #cond-mat.stat-mech #physics.bio-ph #physics.chem-ph
paper · pdf · doi:10.1063/1.4898663
published as J. Chem. Phys. 141, 174704 (2014) · 16 pages, 8 figures
arxiv created 2014/09/09 · openalex publication_date 2014/11/04 · arxiv updated 2015/06/22 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05
We study the distribution of multivalent counterions next to a dielectric slab, bearing a quenched, random distribution of charges on one of its solution interfaces, with a given mean and variance, both in the absence and in the presence of a bathing monovalent salt solution. We use the previously derived approach based on the dressed multivalent-ion theory that combines aspects of the strong and weak coupling of multivalent and monovalent ions in a single framework. The presence of quenched charge disorder on the charged surface of the dielectric slab is shown to substantially increase the density of multivalent counterions in its vicinity. In the counterion-only model (with no monovalent salt ions), the surface disorder generates an additional logarithmic attraction potential and thus an algebraically singular counterion density profile at the surface. This behavior persists also in the presence of a monovalent salt bath and results in significant violation of the contact-value theorem, reflecting the anti-fragility effects of the disorder that drive the system towards a more "ordered" state. In the presence of an interfacial dielectric discontinuity, depleting the counterion layer at the surface, the charge disorder still generates a much enhanced counterion density further away from the surface. Likewise, the charge inversion and/or overcharging of the surface occur more strongly and at smaller bulk concentrations of multivalent counterions when the surface carries quenched charge disorder. Overall, the presence of quenched surface charge disorder leads to sizable effects in the distribution of multivalent counterions in a wide range of realistic parameters and typically within a distance of a few nanometers from the charged surface.