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[hal-01360415] A variational approach to the liquid-vapor phase transition for hardcore ions in the bulk and in nanopores.

(15/06/2021)  
We employ a field-theoretical variational approach to study the behavior of ionic solutions in the grand canonical ensemble. To describe properly the hardcore interactions between ions, we use a cutoff in Fourier space for the electrostatic contribution of the grand potential and the Carnahan-Starling equation of state with a modified chemical potential for the pressure one. We first calibrate our method by comparing its predictions at room temperature with Monte Carlo results for excess chemical potential and energy. We then validate our approach in the bulk phase by describing the classical “ionic liquid-vapor” phase transition induced by ionic correlations at low temperature, before applying it to electrolytes at room temperature confined to nanopores embedded in a low dielectric medium and coupled to an external reservoir of ions. The ionic concentration in the nanopore is then correctly described from very low bulk concentrations, where dielectric exclusion shifts the transition up to room temperature for sufficiently tight nanopores, to high concentrations where hardcore interactions dominate which, as expected, modify only slightly this ionic “capillary evaporation.”

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Cosmology Hydrodynamics Gravitation collapse Chemotaxie Turbulence Phase separation Black hole Metastable states Wave function Keller-Segel Energy high Polytrope Structure Random walker Field theory scalar DNA Entropy Random tilings Collapse Atmosphere Persistence 9536+x Dissipation Catastrophe theory 9535+d Gravitation self-force Membrane transport Critical phenomena Poisson equation Dark matter Scalar field theory Phase transition Statistical mechanics TASEP Denaturation Fermi gas 9880-k General relativity Einstein 9862Gq Interacting agents Dark matter halo Scattering length Nonrelativistic Temperature Suppression Brownian motion Chemotaxis Nanofiltration Scalar field Théorème du viriel Collisionless stellar-systems Transition vitreuse Game theory Potential quantum Self-organization Smoluchowski-Poisson Long-range interactions Euler-Maclaurin Bose–Einstein condensates Quasicrystals Gravitational collapse Diffusion Smoluchowski equation Formation Quantum chromodynamics axion Glass transition Thermodynamics Dark matter condensation Fokker-Planck Marcheur aléatoire Violent relaxation Numerical calculations Virial theorem Evaporation Random process Parametrization Axion star Statistical and Nonlinear Physics Statistical Mechanics Physique statistique Rotation Mouvement brownien Condensation Bose-Einstein Effondrement gravitationnel Ions close to interfaces Perturbation theory Stability Computational modelling Self-gravitating systems Wisdom of crowds Bethe ansatz Generalized thermodynamics Processus stochastique Competition 9530Sf Cosmological model Gravitation Axion Quantum mechanics