Brownian dynamics simulations and Ornstein-Zernike equation for charged fluids using the Wolf potential

• Published in: Journal of molecular liquids Vol. 390; p. 123106
• Main Authors: Pérez-Hernández, Fidencio, Contreras-Aburto, Claudio, Falcón-González, José Marcos, Gil-Villegas, Alejandro, Castañeda-Priego, Ramón
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15.11.2023
• Subjects: Brownian dynamics; Charged colloidal dispersions; Dynamical properties; Primitive model; Strong electrolytes; Wolf potential; Wolf potential; Dynamical properties; Strong electrolytes; Brownian dynamics; 11K45; 00A79; Primitive model; Charged colloidal dispersions
• ISSN: 0167-7322; 1873-3166
• DOI: 10.1016/j.molliq.2023.123106

From a computational point of view, a promising description for charged-stabilized fluids is the so-called Wolf method, which is faster than the standard Ewald summation technique. Using Monte Carlo computer simulations, it was recently shown that the static correlation functions of strong electrolytes obtained with the Wolf potential satisfy the Stillinger–Lovett sum rules, which are a consequence of perfect screening, and are directly related to the local electroneutrality condition and the electrostatic screening within the Debye–Hückel regime. In this contribution, the Wolf potential is adapted to Brownian dynamics simulations to study both the structural and dynamical properties of charged fluids. In addition, we have solved the Ornstein-Zernike equation with the Wolf potential using the HNC closure relation. The resulting radial distributions agree well with the simulation data and previous results obtained with the Ewald technique. Simulation results using Brownian dynamics for weakly charged colloidal dispersions and asymmetric electrolytes are presented. The results include mean square displacement, self-intermediate scattering, and shear relaxation function, with no consideration of hydrodynamic interactions. Including the Wolf potential in Brownian dynamics simulations opens up the possibility of studying interesting transport phenomena in the low Reynolds and Peclet regime, even in those cases where hydrodynamic interactions become relevant. •Brownian dynamics simulations for charge-stabilized fluids using the Wolf potential are presented.•The solution of the Ornstein-Zernike equation with the Wolf potential is obtained.•The microstructure of asymmetric electrolytes and weakly charged colloids is reported.•The transport properties of ionic fluids are determined by means of Brownian dynamics simulations.