Like-Charge Attraction at the Nanoscale: Ground-State Correlations and Water Destructuring

• Published in: The journal of physical chemistry. B Vol. 126; no. 16; pp. 3143 - 3149
• Main Authors: Palaia, Ivan, Goyal, Abhay, Del Gado, Emanuela, Šamaj, Ladislav, Trizac, Emmanuel
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 28-04-2022
• Subjects: B: Soft Matter, Fluid Interfaces, Colloids, Polymers, and Glassy Materials; Ions; Monte Carlo Method; Physics; Solvents; Static Electricity; Water
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/acs.jpcb.2c00028

Like-charge attraction, driven by ionic correlations, challenges our understanding of electrostatics both in soft and hard matter. For two charged planar surfaces confining counterions and water, we prove that, even at relatively low correlation strength, the relevant physics is the ground-state one, oblivious of fluctuations. Based on this, we derive a simple and accurate interaction pressure that fulfills known exact requirements and can be used as an effective potential. We test this equation against implicit-solvent Monte Carlo simulations and against explicit-solvent simulations of cement and several types of clays. We argue that water destructuring under nanometric confinement drastically reduces dielectric screening, enhancing ionic correlations. Our equation of state at reduced permittivity therefore explains the exotic attractive regime reported for these materials, even in the absence of multivalent counterions.