Static and dynamic theory of polarization under internal and directing electric fields: Fixed-charge and fixed-potential conditions

Abstract

We present a continuum theory on statics and dynamics of polar fluids, where the orientational polarization p1 and the induced polarization p2 are governed by the Onsager directing field Ed and the Lorentz internal field F, respectively. We start with a dielectric free energy functional F with a cross term ∝∫drp1 · p2, which was proposed by Felderhof [J. Phys. C: Solid State Phys. 12, 2423 (1979)]. With this cross-coupling, our theory can yield the theoretical results by Onsager and Kirkwood. We also present dynamic equations using the functional derivatives δF/δpi to calculate the space-time correlations of pi. We then obtain analytic expressions for various frequency-dependent quantities, including the Debye formula. We find that the fluctuations of the total polarization drastically depend on whether we fix the electrode charge or the applied potential difference between parallel metal electrodes. In the latter fixed-potential condition, we obtain a nonlocal (long-range) polarization correlation inversely proportional to the cell volume V, which is crucial to understanding the dielectric response. It is produced by nonlocal charge fluctuations on the electrode surfaces and is sensitive to the potential drops in the Stern layers in small systems. These nonlocal correlations in the bulk and on the surfaces are closely related due to the global constraint of fixed potential difference. We also add some results in other boundary conditions, including the periodic one, where nonlocal correlations also appear.