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The structure and thickness of the electrical double layer (EDL) at carbon electrodes strongly influence electrochemical performance, yet remain poorly understood in super-concentrated aqueous electrolytes. Here we combine classical and…

The structure of cylindrical double layers is studied using a modified Poisson Boltzmann theory and the density functional approach. In the model double layer, the electrode is a cylindrical polyion that is infinitely long, impenetrable,…

Soft Condensed Matter · Physics 2013-12-18 V. Dorvilien , C. N. Patra , L. B. Bhuiyan , C. W. Outhwaite

We have developed a molecular mean-field theory -- fourth-order Poisson-Nernst-Planck-Bikerman theory -- for modeling ionic and water flows in biological ion channels by treating ions and water molecules of any volume and shape with…

Soft Condensed Matter · Physics 2020-05-18 Jinn-Liang Liu , Bob Eisenberg

We present a nonlocal electrostatic formulation of nonuniform ions and water molecules with interstitial voids that uses a Fermi-like distribution to account for steric and correlation effects in electrolyte solutions. The formulation is…

Soft Condensed Matter · Physics 2017-03-27 Jinn-Liang Liu , Dexuan Xie , Bob Eisenberg

The Debye-H\"uckel equation is a fundamental physical model in chemical thermodynamics that describes the free energy (chemical potential, activity) of an ion in electrolyte solutions at variable salt concentration, temperature, and…

Chemical Physics · Physics 2018-11-14 Chin-Lung Li , Jinn-Liang Liu

The equilibrium electric double layer (EDL) that surrounds the colloidal particles is determinant for the response of a suspension under a variety of static or alternating external fields. An ideal salt-free suspension is composed by the…

Soft Condensed Matter · Physics 2017-09-13 R. Roa , F. Carrique , E. Ruiz-Reina

Three analytic results are proposed for a linear form of the modified Poisson-Boltzmann equation in the theory of bulk electrolytes. Comparison is also made with the mean spherical approximation results. The linear theories predict a…

Statistical Mechanics · Physics 2019-06-28 C. W. Outhwaite , L. B. Bhuiyan

The Bragg-Williams free energy is used to incorporate nearest-neighbor interactions into the lattice gas model of a solvent-free ionic liquid near a planar electrode. We calculate the differential capacitance from solutions of the…

Chemical Physics · Physics 2018-12-04 Rachel Downing , Bjorn K. Berntson , Guilherme V. Bossa , Sylvio May

In this work a dynamical system approach is taken to systematically investigate the one-dimensional classical Poisson-Boltzmann (PB) equation with various boundary conditions. This framework, particularly, the phase space portrait, has a…

Classical Analysis and ODEs · Mathematics 2024-07-01 Kaiyin Huang , Weishi Liu

We formulate a general mean-field theory of a flat electric double layer in ionic liquids and electrolyte solutions with ions possessing static polarizability and a permanent dipole moment on a charged electrode. We establish a new…

Statistical Mechanics · Physics 2021-08-17 Yu. A. Budkov , S. V. Zavarzin , A. L. Kolesnikov

Poisson-Boltzmann (PB) theory is the classic approach to soft matter electrostatics which has been applied to numerous problems of physical chemistry and biophysics. Its essential limitations are the neglect of correlation effects and of…

Soft Condensed Matter · Physics 2016-08-03 Sahin Buyukdagli , Ralf Blossey

The electric double layer structure in an electrolyte close to a solid substrate near the three-phase contact line is approximated by considering the linearized Poisson-Boltzmann equation in a wedge geometry. The mathematical approach…

Soft Condensed Matter · Physics 2012-09-03 Aaron Dörr , Steffen Hardt

The effective electrostatic interaction between a pair of colloids, both of them located close to each other at an electrolyte interface, is studied by employing the full, nonlinear Poisson-Boltzmann (PB) theory within classical density…

Soft Condensed Matter · Physics 2016-08-17 Arghya Majee , Markus Bier , S. Dietrich

Three-dimensional two-layer incompressible Euler fluids are studied from a Hamiltonian perspective. A natural Hamiltonian structure for the effective 2D model described by the interface-value of the field variables is obtained by means of a…

Mathematical Physics · Physics 2026-04-27 R. Camassa , G. Falqui , G. Ortenzi , M. Pedroni , E. Sforza

The combinatorial explosion of empirical parameters in tens of thousands presents a tremendous challenge for extended Debye-H\"uckel models to calculate activity coefficients of aqueous mixtures of most important salts in chemistry. The…

Soft Condensed Matter · Physics 2018-03-14 Jinn-Liang Liu , Bob Eisenberg

The electrical double layer (EDL) at aqueous solution-metal oxide interfaces critically affects many fundamental processes in electrochemistry, geology and biology, yet understanding its microscopic structure is challenging for both theory…

Classical theory of the electric double layer is based on the fundamental assumption of a dilute solution of point ions. There are a number of situations such as high applied voltages, high concentration of electrolytes, systems with…

Fluid Dynamics · Physics 2015-06-11 Brian D. Storey , Martin Z. Bazant

Electric double layer (EDL) formation underlies the functioning of supercapacitors and several other electrochemical technologies. Here, we study how the EDL formation near two flat blocking electrodes separated by $2L$ is affected by…

Chemical Physics · Physics 2025-09-23 David Fertig , Mathijs Janssen

We study theoretically the osmotic pressure of a suspension of charged objects (e.g., colloids, polyelectrolytes, clay platelets, etc.) dialyzed against an electrolyte solution using the cell model and linear Poisson-Boltzmann (PB) theory.…

Soft Condensed Matter · Physics 2009-11-07 Markus Deserno , Hans-Hennig von Grunberg

Constant-potential molecular dynamics (MD) simulations are indispensable for understanding the capacitance, structure, and dynamics of electrical double layers (EDLs) at the atomistic level. However, the classical constant-potential method,…