Percolation transitions in compressed SiO₂ glasses

Amorphous-amorphous transformations under pressure are generally explained by changes in the local structure from low- to higher-fold coordinated polyhedra^1-4. However, as the notion of scale invariance at the critical thresholds has not been addressed, it is still unclear whether these transformations behave similarly to true phase transitions in related crystals and liquids. Here we report ab initio-based calculations of compressed silica (SiO₂) glasses, showing that the structural changes from low- to high-density amorphous structures occur through a sequence of percolation transitions. When the pressure is increased to 82 GPa, a series of long-range ('infinite') percolating clusters composed of corner- or edge-shared tetrahedra, pentahedra and eventually octahedra emerge at critical pressures and replace the previous 'phase' of lower-fold coordinated polyhedra and lower connectivity. This mechanism provides a natural explanation for the well-known mechanical anomaly around 3 GPa, as well as the structural irreversibility beyond 10 GPa, among other features. Some of the amorphous structures that have been discovered mimic those of coesite IV and V crystals reported recently^5,6, highlighting the major role of SiO₅ pentahedron-based polyamorphs in the densification process of vitreous silica. Our results demonstrate that percolation theory provides a robust framework to understand the nature and pathway of amorphous-amorphous transformations and open a new avenue to predict unravelled amorphous solid states and related liquid phases^7,8.