2020/07/31 by Thomas Sayer, Stephen J. Cox · 16 citations
Chemistry · Energy · Physics and Astronomy · #Charge (physics) #Charge density #Displacement (psychology) #Electric field #Electrolyte #Electrostatics and Colloid Interactions #Ion #Iron oxide chemistry and applications #Slab #Spectroscopy and Quantum Chemical Studies #Surface (topology) #Surface charge #cond-mat.mtrl-sci
paper · pdf · doi:10.1063/5.0022596
published in The Journal of Chemical Physics 153(16), 164709 (American Institute of Physics) · Main paper: 8 pages; 4 figures. Supporting Info: 2 pages; 2 figures
openalex created_date 2020/07/23 · arxiv created 2020/09/21 · openalex publication_date 2020/10/27 · arxiv updated 2021/03/25 · openalex updated_date 2026/08/05
Attaining accurate average structural properties in a molecular simulation should be considered a prerequisite if one aims to elicit meaningful insights into a system's behavior. For charged surfaces in contact with an electrolyte solution, an obvious example is the density profile of ions along the direction normal to the surface. Here, we demonstrate that, in the slab geometry typically used in simulations, imposing an electric displacement field D determines the integrated surface charge density of adsorbed ions at charged interfaces. This allows us to obtain macroscopic surface charge densities irrespective of the slab thickness used in our simulations. We also show that the commonly used Yeh-Berkowitz method and the "mirrored slab" geometry both impose vanishing integrated surface charge densities. We present results both for relatively simple rocksalt (1 1 1) interfaces and the more complex case of kaolinite's basal faces in contact with an aqueous electrolyte solution.