Conductivity of electrolyte solutions: self-consistent Debye–Hückel–Onsager theory

Physical Chemistry Chemical Physics. 2026. Vol. 28. No. 11. P. 6756–6768.

Yury A. Budkov, Nikolai N. Kalikin

This study presents a novel approach to addressing the limitations in understanding the behavior of charged particles in solutions. The approach is based on the development of the Self-Consistent Debye–Hückel–Onsager (SCDHO) theory, which integrates the effects of non-local charge distributions using a Slater-type charge form factor model. This results in a modified Coulomb potential at short distances, unlike traditional approaches such as the classical Debye–Hückel–Onsager theory. The proposed method relies on explicit expressions derived from gradients of local chemical potentials rooted in classical density functional theory (DFT) and the Ornstein–Zernike formalism for correlation functions. Our theoretical framework enables the derivation of analytic equations that describe both correlation (aka relaxation) and electrophoretic contributions to total electric conductivity. Within the established theoretical framework, the model of smeared charges with Slater-type charge form factors provides an accurate predictive tool that can be applied to a wide range of ion valences, concentrations, and temperatures, including both aqueous and non-aqueous electrolyte solutions.

Keywords: electric conductivity, корреляционные функции, Classical density functional theory, Теория классического функционала плотности, электропроводность, electrolytes, электролиты, correlation functions

Publication based on the results of: Прогнозирование свойств молекулярных систем: совмещение методов машинного обучения и классических методов моделирования (2026)