Variational functional theory for coulombic correlations in the electric double layer

Abstract

A classical coulombic correlation functional in one-loop (1L) and local-density-approximation (LDA) is derived for electrolyte solutions, starting from a first-principles many-body partition function. The 1L-LDA functional captures correlations between electrolyte ions and solvent dipoles, such as screening and solvation, that are ignored by conventional mean-field theories. This 1L-LDA functional introduces two parameters that can be tuned to the experimental dielectric permittivity and activity coefficients in the bulk electrolyte solution. The capabilities of the 1L-LDA functional for the description of metal-electrolyte interfaces are demonstrated by embedding the functional into a combined quantum-classical model. Here, the 1L-LDA functional leads to a more pronounced double-peak structure of the interfacial capacitance with higher peaks and shorter peak-to-peak distance, significantly improving the agreement with experimental data and showing that electrolyte correlation effects exert a vital impact on the capacitive response.

References in corpus (14)

• Double layer in ionic liquids: Overscreening vs. crowding
• Steric Effects in Electrolytes: A Modified Poisson-Boltzmann Equation
• Grand canonical electronic density-functional theory: algorithms and applications to electrochemistry
• Beyond Poisson-Boltzmann: Fluctuations and Correlations
• Dipolar Poisson-Boltzmann Equation: Ions and Dipoles Close to Charged Surfaces
• The Dielectric Constant of Ionic Solutions: A Field-Theory Approach
• Computing Counterion Densities at Intermediate Coupling
• Joint density-functional theory for electronic structure of solvated systems
• Molecular Density Functional Theory of Water
• Dielectric Constant of Ionic Solutions: Combined Effects of Correlations and Excluded Volume
• A computationally efficacious free-energy functional for studies of inhomogeneous liquid water
• Nonlinear Dielectric Decrement of Electrolyte Solutions: an Effective Medium Approach
• The Primitive Model in Classical Density Functional Theory: Beyond the Standard Mean-Field Approximation
• First-principles theory of electrochemical capacitance

Cited by in corpus (2)

• Brownian dynamics simulations of electric double-layer capacitors with tunable metallicity
• Classical theory of electron-ion correlations at electrochemical interfaces: Closing the circuit from double-layer charging to ion adsorption