The Cationic Energy Landscape in Alkali Silicate Glasses: Properties and Relevance

Lammert H, Banhatti RD, Heuer A

Abstract

Individual cationic site energies are explicitly determined from molecular dynamics simulations of alkali silicate glasses, and the properties and relevance of this local energetics to ion transport are studied. The absence of relaxations on the time scale of ion transport proves the validity of a static description of the energy landscape, as it is generally used in hopping models. The Coulomb interaction among the cations turns out to be essential to obtain an average energy landscape in agreement with typical simplified hopping models. Strong correlations exist both between neighboring sites and between different energetic contributions at one site, and they shape essential characteristics of the energy landscape. A model energy landscape with a single vacancy is used to demonstrate why average site energies, including the full Coulomb interaction, are still insufficient to describe the site population of ions, or their dynamics. This model explains how the relationship between energetics and ion dynamics is weakened, and thus establishes conclusively that a hopping picture with static energies fails to capture all the relevant information. It is therefore suggested that alternative simplified models of ion conduction are needed.