Global space correlations of polarization, charge density, and electric field in electrolytes under the fixed-potential condition

Abstract

We examine the thermal fluctuations of the polarization $p$, the charge density $\rho$, and the electric field $E$ in dilute electrolytes inserted between pararell metallic electrodes, where we fix the applied potential difference $\Phi_a$ between the two electrodes. If the film thickness $H$ is shorter than the Debye screening length $\kappa^{-1}$, the space correlation of the polarization $p_z$ and the electric field $E_z$ along the surface normal (in the $z$ direction) acuire global components inversely proportional to the film volume $V$, which vary slowly along the $z$ axis and are homogeneous in the $xy$ plane. The areal charge density on each electrode surface also has a component homogeneous on the surface, which produces the global electric fluctuations. On the other hand, if $H$ much exceeds $\kappa^{-1}$, the global correlations of $p_z$ and $\rho$ become small in the bulk region outside the electric double layers, but that of $E_z$ remains almost unchanged by ions in the whole cell at fixed $\Phi_a$. The dielectric constant $\epsilon_{\rm eff}$ depends on $H$ and $\kappa$ and is expressed in terms of the fluctuation variances of $p_z$ and $\rho$ and that of the noblocal surface charge density at fixed $\Phi_a$.