Mechanism of overscreening breakdown by molecular-scale electrode surface morphology in asymmetric ionic liquids

Nesterova, Irina; Evstigneev, Nikolay M.; Ryabkov, Oleg I.; Gerke, Kirill M.; Khlyupin, Aleksey

doi:10.1016/j.jcis.2024.08.040

Journal of Colloid and Interface Science

2025

DOI: 10.1016/j.jcis.2024.08.040

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Mechanism of overscreening breakdown by molecular-scale electrode surface morphology in asymmetric ionic liquids

Irina Nesterova,

Nikolay M. Evstigneev,

Oleg I. Ryabkov

et al.

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Cited by 2 publications

References 43 publications

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Thermomechanical approach to calculating mechanical stresses in inhomogeneous fluids and its applications to ionic fluids

Budkov,

Kalikin,

Brandyshev

2024

J. Stat. Mech.

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This extended article presents a thermomechanical approach for calculating the stress tensor from the thermodynamic potential of inhomogeneous fluids and some applications to ionic fluids. The technique, based on the invariance of the fluid’s thermodynamic potential with respect to spatial transformations of translation and rotation, offers an alternative to the general covariant approach developed by two of the authors. We apply this technique to both pure mean-field theories of fluids in general and a theory that includes thermal fluctuations of the order parameter, using the example of ionic fluids. Additionally, we apply the thermomechanical approach to fluid models with vector order parameters, such as liquid dielectrics. For this case, we obtain a general expression for the stress tensor. Furthermore, we discuss specific issues related to the calculation of disjoining pressure in ionic fluids confined in nanoscale slit-like pores with metal or dielectric walls, using the Coulomb gas model. To test the robustness of the proposed approach, we reproduce a number of known results from the statistical theory of inhomogeneous fluids and obtain several new ones.

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Thermomechanical approach to calculating mechanical stresses in inhomogeneous fluids and its applications to ionic fluids

Budkov,

Kalikin,

Brandyshev

2024

J. Stat. Mech.

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Incorporation of charge discreteness and ion correlations into lattice models of ionic liquids

Bossa,

May

2024

Front. Chem.

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Lattice-based mean-field models of ionic liquids neglect charge discreteness and ion correlations. To address these limitations, we propose separating the short-range and long-range parts of the electrostatic interaction by truncating the Coulomb potential below a fixed distance that is equal to or slightly larger than that between neighboring ions. Interactions and correlations between adjacent ions can then be modeled explicitly, whereas longer-ranged electrostatic interactions are captured on the mean-field level. We implement this approximation into the framework of modeling a compact, solvent-free ionic liquid by, first, considering terms up to the fourth order of the operator that represents the truncated Coulomb potential and, second, by accounting for electrostatic correlations between pairs of neighboring ions on the level of the quasi-chemical approach. A set of boundary conditions for the resulting self-consistent fourth-order differential equation follows from functional minimization of the free energy. The differential capacitance of an ionic liquid in contact with a planar electrode is calculated analytically up to quadratic order in the electrode’s surface charge density by solving the linearized model and applying a perturbation approach valid beyond the linear regime. We demonstrate that charge discreteness enhances the differential capacitance, whereas electrostatic correlations between ion–ion pairs drive the transition from a bell-shaped to a camel-shaped profile of differential capacitance. Our approach offers a systematic way to further improve the treatment of charge discreteness, account for short-range electrostatic and non-electrostatic interactions, and include higher-order ion–ion correlations.

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Mechanism of overscreening breakdown by molecular-scale electrode surface morphology in asymmetric ionic liquids

Cited by 2 publications

References 43 publications

Thermomechanical approach to calculating mechanical stresses in inhomogeneous fluids and its applications to ionic fluids

Thermomechanical approach to calculating mechanical stresses in inhomogeneous fluids and its applications to ionic fluids

Incorporation of charge discreteness and ion correlations into lattice models of ionic liquids

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