Temperature dependence of spatially heterogeneous dynamics in a model of viscous silica

Abstract

Molecular dynamics simulations are performed to study spatially heterogeneous dynamics in a model of viscous silica above and below the critical temperature of the mode coupling theory, T(MCT) . Specifically, we follow the evolution of the dynamic heterogeneity as the temperature dependence of the transport coefficients shows a crossover from non-Arrhenius to Arrhenius behavior when the melt is cooled. It is demonstrated that, on intermediate time scales, a small fraction of oxygen and silicon atoms are more mobile than expected from a Gaussian approximation. These highly mobile particles form transient clusters larger than that resulting from random statistics, indicating that the dynamics are spatially heterogeneous. An analysis of the clusters reveals that the mean cluster size is maximum at times intermediate between ballistic and diffusive motion, and the maximum size increases with decreasing temperature. In particular, the growth of the clusters continues into the crossover to Arrhenius behavior for the transport coefficients. These findings imply that the structural relaxation in silica cannot be understood as a statistical bond breaking process. Although the mean cluster sizes for silica are at the lower end of the spectrum of values reported in the literature for other model liquids, we find that spatially heterogeneous dynamics in models of strong and fragile glass formers are similar on a qualitative level. However, unlike the results for fragile liquids, we show that correlated particle motion along quasi-one-dimensional, stringlike paths is of little importance for the structural relaxation in this model of silica, suggesting that stringlike motion is suppressed by the presence of a network structure. To study transient clusters of localized particles, we calculate a generalized susceptibility corresponding to the self-part of a four-point time dependent density correlation function. We find that this generalized susceptibility is maximum on the time scale of the structural relaxation, where a strong increase of the peak height indicates a growing length of spatial correlations between localized particles upon cooling. Characterizing the local structural environments of the most mobile and the most immobile particles, respectively, we show that high particle mobility is facilitated by, but not limited to, the vicinity of defects in the network structure.