Comparison of ion sites and diffusion paths in glasses obtained by molecular dynamics simulations and bond valence analysis

TL;DR

This study compares molecular dynamics and bond valence analysis for identifying lithium ion sites and diffusion paths in glasses, finding bond valence estimates the number of sites but poorly locates diffusion pathways.

Contribution

It introduces a modified bond valence mismatch approach that improves the estimation of diffusion paths in amorphous lithium silicate glasses.

Findings

Bond valence method estimates the number of sites but poorly locates diffusion paths.

Modified valence mismatch improves identification of diffusion pathways.

Regions identified by bond valence can capture up to 90% of the diffusion path.

Abstract

Based on molecular dynamics simulations of a lithium metasilicate glass we study the potential of bond valence sum calculations to identify sites and diffusion pathways of mobile Li ions in a glassy silicate network. We find that the bond valence method is not well suitable to locate the sites, but allows one to estimate the number of sites. Spatial regions of the glass determined as accessible for the Li ions by the bond valence method can capture up to 90% of the diffusion path. These regions however entail a significant fraction that does not belong to the diffusion path. Because of this low specificity, care must be taken to determine the diffusive motion of particles in amorphous systems based on the bond valence method. The best identification of the diffusion path is achieved by using a modified valence mismatch in the BV analysis that takes into account that a Li ion favors equal partial valences to the neighboring oxygen ions. Using this modified valence mismatch it is possible to replace hard geometric constraints formerly applied in the BV method. Further investigations are necessary to better understand the relation between the complex structure of the host network and the ionic diffusion paths.