Debye–Hückel approximation ($({\nabla }^2-{\kappa }_D^2)\varphi =-{\rho }_{\mathrm{fixed}}/\epsilon$)

The Debye–Hückel approximation linearizes mobile-ion Boltzmann densities about a neutral bulk electrolyte. It is valid for ionic potential energies small compared with $k_{B}T$. The inverse Debye–Hückel screening length satisfies ${\kappa }_D^2={\sum }_i{n}_i{z}_i^2{e}^2/(\epsilon k_{B}T)$. The quadratic screened charging free energy includes both electric field energy and the linearized ionic-response term $\epsilon {\kappa }_D^2{\varphi }^2/2$.

A lateral sinusoidal surface charge density with wave number $k$ in the Debye–Hückel approximation generates vertical exponential or hyperbolic functions with inverse length $p=\sqrt{k^2+{\kappa }_D^2}$. In a homogeneous electrolyte filling all space, an isolated sheet at $z_s$ produces $\varphi ={\sigma }_k(x)e^{-p|z-z_s|}/(2\epsilon p)$. Boundary conditions determine the normalization when the electrolyte occupies only a gap.

Two equally modulated charge sheets in identical full-space electrolyte have charging energy per area ${\alpha }^2[1+e^{-pd}\cos \theta ]/(4\epsilon p)$, where $p=\sqrt{k^2+{\kappa }_D^2}$. Its phase-dependent interaction favors a half-wavelength offset, with opposite charge patches facing each other. For an electrolyte gap with negligible exterior displacement response, the energy is instead ${\alpha }^2[\coth (pd)+\cos \theta /\sinh (pd)]/(2\epsilon p)$, with the same minimizing phase. Absolute energies require specified exterior electrostatic interface boundary conditions.