The infra-red absorption of ionic crystals differs in important details from the predictions of the theory based on first approximations. It is known that this discrepancy may be due to two effects which are neglected in such a theory, namely, to the anharmonic terms in the potential energy and to those terms in the dipole moment which are of higher order than the first in the displacement co-ordinates. These higher-order terms in the dipole moment arise from the deformation of the electron shells. The present paper develops in a systematic way the influence of these higher-order effects on the static dielectric constant. Because of the dispersion relations, the terms occurring in the static dielectric constant must also appear in the infra-red absorption spectrum . It is found that the third- and the fourth-order potential, the second- and the third-order dipole moment, and cross-terms between the second-order moment and the third-order potential, all contribute terms in the same order to the static dielectric constant. It is also found that the third-order potential contains important contributions from the long-range dipolar interaction. These dipolar contributions are proportional to the product of the first- and second-order dipole moments, and it follows that in ionic crystals a large second-order moment automatically results in a large third-order potential. It is suggested that these dipolar contributions to the third-order potential may be responsible for the fact that in the infra-red spectra of different ionic crystals not only the intensity of the side band but also the width of the main band varies in the same way as the deformability of the electron shells.
Dielectric Saturation in Ionic Crystals. II. Deformable Ions