Continuum model of the simple dielectric fluid: Consistency between density based and continuum mechanics methods

Abstract

The basic continuum model for polar fluids is deceptively simple. The free energy integral consists of four terms: The coupling of polarization to an external field, the electrostatic energy of the induced electric field interacting with itself and the stored polarization energy quadratic in the polarization. A local function of density accounts for the mechanical state of the fluid. Viewed as a non-equilibrium free energy functional of number density and polarization, minimization in these two densities under constraints of the Maxwell field equations should lead the correct equilibrium state. The alternative is a continuum mechanics approach in which the mechanical degree of freedom is extended to full deformation. We show that the continuum electromechanics method leads to a force balance equation which is consistent with the density functional equilibrium equation. The continuum mechanics procedure is significantly more demanding. The gain is a well defined pressure tensor derived from deformation of total energy. This resolves the issue of the uncertainty in the pressure tensor obtained from integration of the force density, which is the conventional method in density based thermomechanics. Our derivation is based on the variational electrostatics approach developed by Ericksen (Arch. Rational Mech. Anal. {\bf 183} 299 (2007)).

preprint 33 pages, no figures

References in corpus (6)

• Molecular Density Functional Theory of Water
• Computing the dielectric constant of liquid water at constant dielectric displacement
• Efficient molecular density functional theory using generalized spherical harmonics expansions
• Solvation of complex surfaces via molecular density functional theory
• Electromechanics of the liquid water vapour interface
• Gaussian field model for polar fluids as a function of density and polarization: toward a model for water