First-principles molecular dynamics simulations of anorthite (CaAl2Si2O8) glass at high pressure

We report first-principles molecular dynamics study of the equation of state, structural, and elastic properties of CaAl2Si2O8 glass at 300 K as a function of pressure up to 155 GPa. Our results for the ambient pressure glass show that: (1) as with other silicates, Si atoms remain mostly (> 95%) under tetrahedral oxygen surroundings; (2) unlike anorthite crystal, presence of high-coordination (> 4) Al atoms with similar to 30% abundance; (3) and significant presence of both non-bridging (8%) and triply (17%) coordinated oxygen. To achieve the glass configurations at various pressures, we use two different simulation schedules: cold and hot compression. Cold compression refers to sequential compression at 300 K. Compression at 3000 K and subsequent isochoric quenching to 300 K is considered as hot compression. At the initial stages of compression (0-10 GPa), smooth increase in bond distance and coordination occurs in the hot-compressed glass. Whereas in cold compression, Si (also Al to some extent) displays mainly topological changes (without significantly affecting the average bond distance or coordination) in this pressure interval. Further increase in pressure results in gradual increases in mean coordination, with Si-O (Al-O) coordination eventually reaching and remaining 6 (6.5) at the highest compression. Similarly, the ambient pressure Ca-O coordination of 5.9 increases to 9.5 at 155 GPa. The continuous pressure-induced increase in the proportion of oxygen triclusters along with the appearance and increasing abundance of tetrahedral oxygens results in mean O-T (T = Si and Al) coordination of > 3 from a value of 2.1 at ambient pressure. Due to the absence of kinetic barrier, the hot-compressed glasses consistently produce greater densities and higher coordination numbers than the cold compression cases. Decompressed glasses show irreversible compaction along with retention of high-coordination species when decompressed from pressure ae 10 GPa. The different density retention amounts (12, 17, and 20% when decompressed from 12, 40, and 155 GPa, respectively) signifies that the degree of irreversibility depends on the peak pressure of decompression. The calculated compressional and shear wave velocities (5 and 3 km/s at 0 GPa) for the cold-compressed case display sluggish pressure response in the 0-10 GPa interval as opposed to smooth increase in the hot-compressed one. Shear velocity saturates rather rapidly with a value of similar to 5 km/s, whereas compressional wave velocity displays continuous increase, reaching/exceeding 12.5 km/s at 155 GPa. These structural details suggest that the pressure response of the cold-compressed glasses is not only inherently different at the 0-10 GPa interval, the density, coordination, and wave velocity data are consistently lower than the hot-compressed glasses. Hot-compressed glasses may, therefore, be the better analog in the study of high-pressure silicate melts.