Two-Scale Analysis of the Electrostatics of Dielectric Crystals: Emergence of Polarization Density and Boundary Charges

Abstract

Ionic crystals, such as solid electrolytes and complex oxides, are central to modern technologies for energy storage, sensing, actuation, and other functional applications. An important fundamental issue in the atomic and quantum-scale modeling of these materials is defining the macroscopic polarization. In a periodic crystal, the usual definition of the polarization as the first moment of the charge density in a unit cell is found to depend qualitatively - allowing even a change in the sign - and quantitatively on the choice of unit cell. We examine this issue using a rigorous approach based on the framework of 2-scale convergence. By examining the continuum limit of when the lattice spacing is much smaller than the characteristic dimensions of the body, we show that the 2-scale limit provides both a bulk polarization as well as a surface charge density supported on the boundary of the body. Further, different choices of the periodic unit cell of the body lead to correspondingly different partial unit cells at the boundary; these choices give to different bulk polarization and surface charges but compensate such that the electric field and energy are independent of the choice of unit cell.