The statistical mechanics of the electrical double layer: Stress tensor and contact conditions

Abstract

The aim of this paper is twofold: (i) to clarify the definition of the mechanical (hydrostatic) stress tensor and the Maxwell (electrostatic) stress tensor in nonuniform electrolytes or Coulombic systems, and (ii) to derive contact conditions for an electrolyte at a charged hard wall to include (a) ion size effects, (b) imaging effects at the wall, and (c) effects due to the molecular nature of the solvent (the civilized model). The last result is valid for a general nonlinear dielectric whose molecules can have any electrostatic multipole interactions. © 1981 American Institute of Physics.