Solution Structure Effects on the Properties of Electric Double Layers with Surface Charge Regulation Assessed by Density Functional Theory

• Published in: Langmuir Vol. 34; no. 46; pp. 13808 - 13820
• Main Authors: van Swol, Frank B, Petsev, Dimiter N
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 20.11.2018
• Subjects: density functional theory; ions; solvents
• ISSN: 0743-7463; 1520-5827; 1520-5827
• DOI: 10.1021/acs.langmuir.8b02453

The structure of electrolyte solutions in electric double layers is primarily determined by the solvent, despite the fact that it is usually neutral and not subject to Coulombic interactions. The number of solvent molecules in a typical electrolyte solution may be significantly greater that the number of ions. Hence, the charged species compete for space with a much larger number of neutral molecules, which has a strong effect on the density distributions near charged surfaces. Even for very dilute electrolyte solutions, the density profiles resemble liquidlike structure, which is entirely due to the presence of the dense solvent. Our work demonstrates that the solvent structural effect strongly couples to the surface chemistry, which governs the charge and potential. We argue that a comprehensive statistical–mechanical approach, such as classical density functional theory that explicitly includes all solution species, in combination with a surface charge regulation condition at the interface, provides an excellent approach for describing charged interfaces. It allows for revealing important physical features and includes non-Coulombic contributions such as ionic and surface solvation.