Ab initio Simulations of Superionic H2O, H2O2, and H9O4 Compounds

Abstract

Using density functional molecular dynamics simulations, we study the behavior of different hydrogen-oxygen compounds at megabar pressures and several thousands of degrees Kelvin where water has been predicted to occur in superionic form. When we study the close packed hcp and dhcp structures of superionic water, we find that they have comparable Gibbs free energies to the fcc structure that we predicted previously [Phys. Rev. Lett., 110 (2013) 151102]. Then we present a comprehensive comparison of different superionic water candidate structures with P2_1, P2_1/c, P3_121, Pcca, C2/m, and Pa3 symmetry that are based on published ground-state structures. We find that the P2_1 and P2_1/c structures transform into a different superionic structure with P2_1/c symmetry, which at 4000 K has a lower Gibbs free energy than fcc for pressures higher than 22.8 +- 0.5 Mbar. This novel structure may also be obtained by distorting a hcp supercell. Finally we show that H2O2 and H9O4 structures will also assume a superionic state at elevated temperatures. Based on Gibbs free energy calculations at 5000 K, we predict that superionic water decompose into H2O2 and H9O4 at 68.7 +- 0.5 Mbar.