Related papers: Fluctuation Theory of Ionic Solvation Potentials
Simulations of water near extended hydrophobic spherical solutes have revealed the presence of a region of depleted density and accompanying enhanced density fluctuations.The physical origin of both phenomena has remained somewhat obscure.…
We evaluate the exponentially rare fluctuations of the ionic current for a dilute electrolyte by means of macroscopic fluctuation theory. We consider the fluctuating hydrodynamics of a fluid electrolyte described by a stochastic…
We use molecular dynamics simulations in a constant potential ensemble to study the effects of solution composition on the electrochemical response of a double layer capacitor. We find that the capacitance first increases with ion…
Electrostatic correlations and variable permittivity of electrolytes are essential for exploring many chemical and physical properties of interfaces in aqueous solutions. We propose a continuum electrostatic model for the treatment of these…
We derive a microscopic theory for the structural dynamics in the vicinity of the glass transition for a liquid exposed to a one-dimensional periodic potential. The periodic potential breaks translational invariance, in particular, the…
We present an exact field-theoretic formulation for a fluctuating, generally asymmetric, salt density in the presence of a charged plate. The non-linear Poisson-Boltzmann equation is obtained as the saddle-point of our field theory action.…
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…
An alternative derivation of Brownian motion is presented. Instead of supplementing the linearized Navier-Stokes equation with a fluctuating force, we directly assume a Gaussian action functional for solvent velocity fluctuations. Solvating…
We derive a relationship for the electric field dependent ionic conductivity in terms of fluctuations of time integrated microscopic variables. We demonstrate this formalism with molecular dynamics simulations of solutions of differing…
Recent molecular simulation and integral equation results alkali-halide ion pair potentials-of-mean-force in water are discussed. Dielectric model calculations are implemented to check that these models produce that characteristic structure…
We construct a dynamical field theory for noninteracting Brownian particles in the presence of a quenched Gaussian random potential. The main variable for the field theory is the density fluctuation which measures the difference between the…
In this note, we show that the Local Molecular Field theory of Weeks et. al. can be re-derived as an extremum problem for an approximate Helmholtz free energy. Using the resulting free energy as a classical, fluid density functional yields…
At mesoscopic scales electrolyte solutions are modeled by the fluctuating generalized Poisson-Nernst-Planck (PNP) equations [J.-P. P\'eraud et al., Phys. Rev. F, 1(7):074103, 2016]. However, at length and time scales larger than the Debye…
The fluctuation-dissipation theorem is a central theorem in nonequilibrium statistical mechanics by which the evolution of velocity fluctuations of the Brownian particle under a fluctuating environment is intimately related to its…
We study Johnson-Nyquist noise in macroscopically inhomogeneous disordered metals and give a microscopic derivation of the correlation function of the scalar electric potentials in real space. Starting from the interacting Hamiltonian for…
We analytically describe the decay to equilibrium of generic observables of a non-integrable system after a perturbation in the form of a random matrix. We further obtain an analytic form for the time-averaged fluctuations of an observable…
The basic mathematical properties of Green's functions used in statistical mechanics as well as the equations defining these functions and the techniques of solving these equations are reviewed. An approach is presented called the…
A self-consistent mode coupling theory (MCT) with microscopic inputs of equilibrium pair correlation functions is developed to analyze electrolyte dynamics. We apply the theory to calculate concentration dependence of (i) time dependent ion…
Starting with a formally exact diagrammatic kinetic theory for the equilibrium correlation functions of particle density and current fluctuations for a monatomic liquid, we develop a theory for high density liquids whose interatomic…
Based on a Debye-Hueckel approach to the one-component plasma we propose a new free energy for incorporating ionic correlations into Poisson-Boltzmann like theories. Its derivation employs the exclusion of the charged background in the…