Negative density-dependence of the structural relaxation time of liquid silica: insights from a comparative molecular...

In many tetrahedral network-forming liquids, structural relaxation is anomalously accelerated by compression over relatively low pressure ranges. Here, for silica, we study this problem through comparative molecular dynamics simulations using two different models. Under compression, the network structures are compacted by slight tuning of the intertetrahedral bond angles while nearly preserving the unit tetrahedral structure. The consequent structural changes are remarkable for length scales larger than the nearest neighbor ion-pair distances. Accompanying with such structural changes, the interactions of the nearest Si-O pairs remain almost unchanged, whereas those of other ion pairs are, on average, strengthened by the degree of compression. In particular, the enhancement of the net Si-O interactions at the next nearest neighbor distance, which assist an ion in escaping from the potential well, reduces the activation energy, leading to a significant acceleration of structural relaxation. The results of our comparative molecular dynamics simulations are compatible with the scenario proposed by Angell, and further indicate that the structural relaxation dynamics cannot be uniquely determined by the configurations but strongly depends on the details of the coupling between the structure and the interaction.