The available sites for ions in a typical disordered ionic conductor are determined. For this purpose we devised a straightforward algorithm which via cluster analysis identifies these sites from long time ionic trajectories below the glass transition. This is exemplified for a lithium silicate glass $({\mathrm{L}\mathrm{i}}_2\mathrm{O}{)}_x({\mathrm{S}\mathrm{i}\mathrm{O}}_2{)}_{(1-x)}$ for $x=0.5$ and $x=0.1$. We find for both concentrations that the number of sites is only slightly bigger than the number of ions. This result suggests a theoretical description of the dynamics in terms of mobile vacancies as most appropriate. Furthermore, identification of the ionic sites allows one to obtain detailed characteristics of the ionic motion, e.g., quantification of correlated forward-backward jumps.

• Received 13 January 2003

DOI:https://doi.org/10.1103/PhysRevLett.90.215901