The off-center effect on the diffusion coefficient of Cu+ and Li+ in the KCl lattice

It is well known that the diffusion coefficients of the Cu+ cation in the NaCl and KCl lattices exceeds by three or four orders of magnitude the corresponding self-diffusion coefficients in the intrinsic temperature regions. This fast diffusion of the Cu+ has been explained in many papers as an interstitial diffusion although the optical spectra do not confirm the existence of interstitial Cu+. In this paper we propose a new mechanism for fast diffusion. The model assumes that the equilibrium positions of the cationic impurities are noncentral and that the diffusion proceeds by hopping across the potential barrier along the nonlinear paths with the highest probability. The main result shows that the off-center position enhances considerably the diffusion. Theoretical diffusion coefficients have been obtained by modelling the potential barrier. Changes of the configuration entropy and the vibration spectra due to the presence of the noncentral impurity have been included in the model. We proceeded in the Li+ cation case as in the case of Cu+ cation. We emphasize the good agreement of the model with the experimental data and we show that if the impurity is placed close to the central site the due diffusion coefficient is close to that for the cationic self-diffusion. (author). 37 refs, 6 figs, 3 tabs