Stochastic density functional theory for ions in a polar solvent

Abstract

In recent years, the theoretical description of electrical noise and fluctuation-induced effects in electrolytes has gained a renewed interest, enabled by stochastic field theories like stochastic density functional theory (SDFT). Such models, however, treat solvents implicitly, ignoring their generally polar nature. In the present study, starting from microscopic principles, we derive a fully explicit SDFT theory that applies to ions in a polar solvent. These equations are solved to compute observables like dynamic charge structure factors and dielectric susceptibilities. We unveil the relative importance of the different contributions (solvent, ions, cross terms) to the dynamics of electrolytes, which are key to understand the couplings between ions and the fluctuations of their microscopic environment.

References in corpus (28)

• Diamondoid Molecules
• Dipolar Poisson-Boltzmann Equation: Ions and Dipoles Close to Charged Surfaces
• The Dielectric Constant of Ionic Solutions: A Field-Theory Approach
• Scaling behavior for ionic transport and its fluctuations in individual carbon nanotubes
• Hydrodynamics of confined active fluids
• Hydrodynamics of isotropic and liquid crystalline active polymer solutions
• Dielectric Constant of Ionic Solutions: Combined Effects of Correlations and Excluded Volume
• Generalized Langevin equations for a driven tracer in dense soft colloids: construction and applications
• Simulating nanoscale dielectric response
• Low Mach Number Fluctuating Hydrodynamics for Electrolytes
• Long-range fluctuation-induced forces in driven electrolytes
• Conductance of concentrated electrolytes: multivalency and the Wien effect
• Relaxation of the thermal Casimir force between net neutral plates containing Brownian charges
• Quadrupolar ${}^{23}$Na${}^{+}$ NMR Relaxation as a Probe of Subpicosecond Collective Dynamics in Aqueous Electrolyte Solutions
• Kinetic and ion pairing contributions in the dielectric spectra of electrolyte aqueous solutions
• Finite field formalism for bulk electrolyte solutions
• Derivation of the nonlinear fluctuating hydrodynamic equation from underdamped Langevin equation
• Coarse-grained forms for equations describing the microscopic motion of particles in a fluid
• Transient fluctuation-induced forces in driven electrolytes after an electric field quench
• Gaussian field model for polar fluids as a function of density and polarization: toward a model for water
• NMR relaxation rates of quadrupolar aqueous ions from classical molecular dynamics using force-field specific Sternheimer factors
• Mean-field microrheology of a very soft colloidal suspension: inertia induces shear-thickening
• Electric-field-induced oscillations in ionic fluids: a unified formulation of modified Poisson-Nernst-Planck models and its relevance to correlation function analysis
• Transverse density fluctuations around the ground state distribution of counterions near one charged plate: stochastic density functional view
• Casimir force in dense confined electrolytes
• Nonlinear conductivity of aqueous electrolytes: beyond the first Wien effect
• Electroviscous effects of simple electrolytes under shear
• Fluctuating hydrodynamics of dilute electrolyte solutions: systematic perturbation calculation of effective transport coefficients governing large-scale dynamics

Cited by in corpus (3)

• Repulsive thermal van der Waals interaction in multi-species asymmetric electrolytes driven by external electric fields
• Structural and Dynamical Crossovers in Dense Electrolytes
• Solving Lyapunov equations for electrically driven ternary electrolytes -- application to long-range van der Waals interactions