Ab initio constraints on the melting of silica at high pressures up to 500 GPa

The melting curve of pure silica (SiO2) was determined using ab initio density functional theory together with the solid -liquid coexisting approach, thermodynamic integration, and the Z method. The melting curves are consistent with a smooth, slow increase in a large region from 50 GPa (dT/dP ti 15 K/GPa) to about 500 GPa (dT/dP ti 5 K/GPa) without any abrupt changes at around 120 and 300 GPa as seen in some recent experimental and computational studies. The topography of the melting curve above 50 GPa is consistent with a gradual change in the distribution of the Si coordination numbers in the liquid state and the absence of large changes in the density following solid -solid phase transitions. The pair distribution functions show that the structural correlation in the liquid is mainly short range and that the Si -O bond is stiff. The densification of the melt structure with pressure above 50 GPa is therefore due to an increase in seven- and eightfold coordinated silicon.