Prediction of new thermodynamically stable aluminum oxides

Recently, it has been shown that under pressure, unexpected and counterintuitive chemical compounds become stable. Laser shock experiments (A. Rode, unpublished) on alumina (Al(2)O(3)) have shown non-equilibrium decomposition of alumina with the formation of free Al and a mysterious transparent phase. Inspired by these observations, we have explored the possibility of the formation of new chemical compounds in the system Al-O. Using the variable-composition structure prediction algorithm USPEX, in addition to the well-known Al(2)O(3), we have found two extraordinary compounds Al(4)O(7) and AlO(2) to be thermodynamically stable in the pressure ranges 330-443 GPa and above 332 GPa, respectively. Both of these compounds at the same time contain oxide O(2−) and peroxide O(2)(2−) ions, and both are insulating. Peroxo-groups are responsible for gap states, which significantly reduce the electronic band gap of both Al(4)O(7) and AlO(2).