Related papers: Fluctuation Theory of Ionic Solvation Potentials
Employing recent advances in response theory and nonequilibrium ensemble reweighting, we study the dynamic and static correlations that give rise to an electric field-dependent ionic conductivity in electrolyte solutions. We consider…
A classical density functional theory is applied to study solvation of solutes in water. An approx- imate form of the excess functional is proposed for water. This functional requires the knowledge of pure solvent direct correlation…
We study large $n$ expansions for the partition function of a Coulomb gas $$Z_n=\frac 1 {\pi^n}\int_{\mathbb{C}^n}\prod_{1\le i<j\le n}|z_i-z_j|^2\prod_{i=1}^n e^{-nQ(z_i)}\, d^2 z_i,$$ where $Q$ is a radially symmetric confining potential…
Quantifying the statistics of occupancy of solvent molecules in the vicinity of solutes is central to our understanding of solvation phenomena. Number fluctuations in small `solvation shells' around solutes cannot be described within the…
Inhomogeneity of ion correlation widely exists in many physicochemical, soft matter, and biological systems. Here, we apply the modified Gaussian renormalized fluctuation theory to study the classic example of the vapor-liquid interface of…
A Response Function Theory and Scattering Theory applicable to the study of physical properties of systems driven arbitrarily away from equilibrium, specialized for dealing with ultrafast processes and in conditions of space resolution…
In this paper we develop a theory to calculate the solvent mediated interaction potential between solute particles dispersed in a solvent. The potential is a functional of the instantaneous distribution of solute particles and is expressed…
We analyze the fluctuations of an electronic thermal current across an idealized molecular junction. The focus here will be on the spectral features of the resulting heat fluctuations. By use of the Green functionmethod we derive an…
Fluctuation relations allow for the computation of equilibrium properties, like free energy, from an ensemble of non-equilibrium dynamics simulations. Computing them for quantum systems, however, can be difficult, as performing dynamic…
The statistical mechanical basis of the fluctuation theory of mixtures is reviewed. An overview of the statistical mechanical relations between the microscopic properties of a system and its macroscopic properties is presented. The…
A fluctuation law of the energy in freely-decaying, homogeneous and isotropic turbulence is derived within standard closure hypotheses for 3D incompressible flow. In particular, a fluctuation-dissipation relation is derived which relates…
We derive an exact representation of the exchange-correlation energy within density functional theory (DFT) which spawns a class of approximations leading to correct long-range asymptotic behavior. In what amounts to be the simplest…
Near-critical thermodynamics in the hard-sphere (1,1) electrolyte is well described, at a classical level, by Debye-Hueckel (DH) theory with (+,-) ion pairing and dipolar-pair-ionic-fluid coupling. But DH-based theories do not address…
We derive a fluctuation theorem for generalized work distributions, related to bijective mappings of the phase spaces of two physical systems, and use it to derive a two-sided constraint maximum likelihood estimator of their free energy…
The microscopic theory of chemical reactions is based on transition state theory, where atoms or ions transfer classically over an energy barrier, as electrons maintain their ground state. Electron transfer is fundamentally different and…
We present an exact field theoretical representation of an ionic solution made of charged hard spheres. The action of the field theory is obtained by performing a Hubbard-Stratonovich transform of the configurational Boltzmann factor. It is…
By extrapolating the energies of non-relativistic atoms and their ions with up to 3000 electrons within Kohn-Sham density functional theory, we find that the ionization potential remains finite and increases across a row, even as…
The spectral functions are studied in conjunction with the dyadic Green's functions for various media. The dyadic Green's functions are found using the eigenfunction expansion method for homogeneous, inhomogeneous, periodic, lossless,…
The mesoscopic field theory for ionic systems [A. Ciach and G. Stell, J. Mol. Liq. 87, 255 (2000)] is extended to the system with charged boundaries. A very simple expression for the excess grand potential functional of the charge density…
Theories of solvation free energies often involve electrostatic potentials at the position of a solute charge. Simulation calculations that apply cutoffs and periodic boundary conditions based on molecular centers result in center-dependent…