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The Debye-Huckel approximation to the free-energy of a simple fluid is written as a functional of the pair correlation function. This functional can be seen as the Debye-Huckel equivalent to the functional derived in the hyper-netted chain framework by Morita and Hiroike, as well as by Lado. It allows one to obtain the Debye-Huckel integral equation through a minimization with respect to the pair correlation function, leads to the correct form of the internal energy, and fulfills the virial theorem.
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In previous publications [arXiv:1608.08430, arXiv:1704.06502], the authors have proposed Debye-Huckel-approximate free-energy functionals of the pair distribution functions for one-component fluid and two-component plasmas. These functionals yield the corresponding Debye-Huckel integral equations when they are minimized with respect to the pair distribution functions, lead to correct thermodynamic relations and fulfill the virial theorem. In the present addendum, we update our results by providing simpler functionals that have the same properties. We relate these functionals to the approaches of Lado [Phys. Rev. A 8:2548, 1973] and of Olivares and McQuarrie [J. Chem. Phys. 65:3604, 1976]. We also discuss briefly the non-uniqueness issue that is raised by these results.
We present a generalization of the Debye-Huckel free-energy-density functional of simple fluids to the case of two-component systems with arbitrary interaction potentials. It allows one to obtain the two-component Debye-Huckel integral equations through its minimization with respect to the pair correlation functions, leads to the correct form of the internal energy density, and fulfills the virial theorem. It is based on our previous idea, proposed for the one-component Debye-Huckel approach, and which was published recently cite{Piron16}. We use the Debye-Kirkwood charging method in the same way as in cite{Piron16}, in order to build an expression of the free-energy density functional. Main properties of the two-component Debye-Huckel free energy are presented and discussed, including the virial theorem in the case of long-range interaction potentials.
Classical density-functional theory provides an efficient alternative to molecular dynamics simulations for understanding the equilibrium properties of inhomogeneous fluids. However, application of density-functional theory to multi-site molecular fluids has so far been limited by complications due to the implicit molecular geometry constraints on the site densities, whose resolution typically requires expensive Monte Carlo methods. Here, we present a general scheme of circumventing this so-called inversion problem: compressed representations of the orientation density. This approach allows us to combine the superior iterative convergence properties of multipole representations of the fluid configuration with the improved accuracy of site-density functionals. Next, from a computational perspective, we show how to extend the DFT++ algebraic formulation of electronic density-functional theory to the classical fluid case and present a basis-independent discretization of our formulation for molecular classical density-functional theory. Finally, armed with the above general framework, we construct a simplified free-energy functional for water which captures the radial distributions, cavitation energies, and the linear and non-linear dielectric response of liquid water. The resulting approach will enable efficient and reliable first-principles studies of atomic-scale processes in contact with solution or other liquid environments.
Electrostatic interactions between point charges embedded into interfaces separating dielectric media are omnipresent in soft matter systems and often control their stability. Such interactions are typically complicated and do not resemble their bulk counterparts. For instance, the electrostatic potential of a point charge at an air-water interface falls off as $r^{-3}$, where $r$ is the distance from the charge, exhibiting a dipolar behaviour. This behaviour is often assumed to be generic, and is widely referred to when interpreting experimental results. Here we explicitly calculate the in-plane potential of a point charge at an interface between two electrolyte solutions with different dielectric permittivities and Debye screening lengths. We show that the asymptotic behaviour of this potential is neither a dipole, which characterises the potential at air-water interfaces, nor a screened monopole, which describes the bulk behaviour in a single electrolyte solution. By considering the same problem in arbitrary dimensions, we find that the physics behind this difference can be traced to the asymmetric propagation of the interaction in the two media. Our results are relevant, for instance, to understand the physics of charged colloidal particles trapped at oil-water interfaces.
This paper brings further insight into the recently published N-body description of Debye shielding and Landau damping [Escande D F, Elskens Y and Doveil F 2014 Plasma Phys. Control. Fusion 57 025017]. Its fundamental equation for the electrostatic potential is derived in a simpler and more rigorous way. Various physical consequences of the new approach are discussed, and this approach is compared with the seminal one by Pines and Bohm [Pines D and Bohm D 1952 Phys. Rev. 85 338--353].
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