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Incorporating Electrolyte Correlation Effects into Variational Models of Electrochemical Interfaces.

ABSTRACT: We propose a way for obtaining a classical free energy density functional for electrolytes based on a first-principle many-body partition function. Via a one-loop expansion, we include coulombic correlations beyond the conventional mean-field approximation. To examine electrochemical interfaces, we integrate the electrolyte free energy functional into a hybrid quantum-classical model. This scheme self-consistently couples electronic, ionic, and solvent degrees of freedom and incorporates electrolyte correlation effects. The derived free energy functional causes a correlation-induced enhancement in interfacial counterion density and leads to an overall increase in capacitance. This effect is partially compensated by a reduction of the dielectric permittivity of interfacial water. At larger surface charge densities, ion crowding at the interface stifles these correlation effects. While scientifically intriguing already at planar interfaces, we anticipate these correlation effects to play an essential role for electrolytes in nanoconfinement.

SUBMITTER: Bruch N

PROVIDER: S-EPMC10895655 | biostudies-literature | 2024 Feb

REPOSITORIES: biostudies-literature

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Incorporating Electrolyte Correlation Effects into Variational Models of Electrochemical Interfaces.

Bruch Nils N Binninger Tobias T Huang Jun J Eikerling Michael M

The journal of physical chemistry letters 20240213 7

We propose a way for obtaining a classical free energy density functional for electrolytes based on a first-principle many-body partition function. Via a one-loop expansion, we include coulombic correlations beyond the conventional mean-field approximation. To examine electrochemical interfaces, we integrate the electrolyte free energy functional into a hybrid quantum-classical model. This scheme self-consistently couples electronic, ionic, and solvent degrees of freedom and incorporates electro ...[more]

PMID: 38349906

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Project description:This work presents a few variational multiscale models for charge transport in complex physical, chemical and biological systems and engineering devices, such as fuel cells, solar cells, battery cells, nanofluidics, transistors and ion channels. An essential ingredient of the present models, introduced in an earlier paper (Bulletin of Mathematical Biology, 72, 1562-1622, 2010), is the use of differential geometry theory of surfaces as a natural means to geometrically separate the macroscopic domain from the microscopic domain, meanwhile, dynamically couple discrete and continuum descriptions. Our main strategy is to construct the total energy functional of a charge transport system to encompass the polar and nonpolar free energies of solvation, and chemical potential related energy. By using the Euler-Lagrange variation, coupled Laplace-Beltrami and Poisson-Nernst-Planck (LB-PNP) equations are derived. The solution of the LB-PNP equations leads to the minimization of the total free energy, and explicit profiles of electrostatic potential and densities of charge species. To further reduce the computational complexity, the Boltzmann distribution obtained from the Poisson-Boltzmann (PB) equation is utilized to represent the densities of certain charge species so as to avoid the computationally expensive solution of some Nernst-Planck (NP) equations. Consequently, the coupled Laplace-Beltrami and Poisson-Boltzmann-Nernst-Planck (LB-PBNP) equations are proposed for charge transport in heterogeneous systems. A major emphasis of the present formulation is the consistency between equilibrium LB-PB theory and non-equilibrium LB-PNP theory at equilibrium. Another major emphasis is the capability of the reduced LB-PBNP model to fully recover the prediction of the LB-PNP model at non-equilibrium settings. To account for the fluid impact on the charge transport, we derive coupled Laplace-Beltrami, Poisson-Nernst-Planck and Navier-Stokes equations from the variational principle for chemo-electro-fluid systems. A number of computational algorithms is developed to implement the proposed new variational multiscale models in an efficient manner. A set of ten protein molecules and a realistic ion channel, Gramicidin A, are employed to confirm the consistency and verify the capability. Extensive numerical experiment is designed to validate the proposed variational multiscale models. A good quantitative agreement between our model prediction and the experimental measurement of current-voltage curves is observed for the Gramicidin A channel transport. This paper also provides a brief review of the field.

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Incorporating Electrolyte Correlation Effects into Variational Models of Electrochemical Interfaces.

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Incorporating Electrolyte Correlation Effects into Variational Models of Electrochemical Interfaces.

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