Year: 2026
Type: article
Abstract: Electrostatic interactions fundamentally govern the structure and transport of electrolytes. In concentrated electrolytes, however, electrostatic and steric correlations, together with ion-solvent coupling, give rise to complex behavior, such as underscreening, that remains challenging to explain despite extensive theoretical effort. Using molecular dynamics simulations of primitive electrolytes with and without space-filling solvent particles, we elucidate the structural and dynamical crossovers and their connection that emerge with increasing salt concentration. Explicit-solvent electrolytes exhibit a screening transition from a charge-dominated dilute regime to a density-dominated concentrated regime, accompanied by dynamical crossovers in ion self-diffusion and ion-pair lifetimes. These dynamical crossovers display a marked discontinuity, unlike the smoother variation of the screening crossover, which originates from short-range ion-counterion structures. The pronounced growth of ionic clusters leads to a percolation transition only at higher concentrations, whereas the onset of the structural and dynamical crossovers is associated primarily with local ion pairing or small aggregates. Both structural and dynamical behaviors are found to depend sensitively on ion-solvent coupling: implicit-solvent electrolytes exhibit a screening transition between two charge-dominated regimes, accompanied by qualitatively distinct dynamical behavior. Finally, we demonstrate that the diffusion-corrected ion-pair lifetime provides a consistent descriptor linking ionic structure and dynamics across electrolyte systems.
Source: Physical review. E
DOI: 10.1103/t1m7-8qm2
Authors: Daehyeok Kim, Taejin Kwon, Jeongmin Kim
Institutions: Jeju National University, Pusan National University
Language: English
Subfield: Physical and Theoretical Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Awards: G2371412000, G5770715341
OpenAlex ID: W4417028106