Abstract
The author derives a simple expression for the average polarisation P induced by an optic phonon within the Born-Oppenheimer approximation. The calculation for P requires a knowledge of the electronic wavefunctions and energies in both the undistorted crystal and the distorted crystal with a 'frozen-in' optic phonon. The expression is correctly boundary-insensitive and is the proper starting point for the calculation of both linear and non-linear contributions to the polarisation, i.e. effective charges. Specifying a pseudopotential formalism and taking the small displacement limit the author recovers the formula of Vogl (1978) for ZT*. Finally a simple model of a diatomic chain of atoms is discussed to show explicity that anharmonic effects are important if ZT* is large.