Unconventional Stoichiometries of Na–O Compounds at High Pressures

It has been realized that the stoichiometries of compounds may change under high pressure, which is crucial in the discovery of novel materials. This work uses systematic structure exploration and first-principles calculations to consider the stability of different stoichiometries of Na–O compounds with respect to pressure and, thus, construct a high-pressure stability field and convex hull diagram. Four previously unknown stoichiometries (NaO(5), NaO(4), Na(4)O, and Na(3)O) are predicted to be thermodynamically stable. Four new phases (P2/m and Cmc2(1) NaO(2) and Immm and C2/m NaO(3)) of known stoichiometries are also found. The O-rich stoichiometries show the remarkable features of all the O atoms existing as quasimolecular O(2) units and being metallic. Calculations of the O–O bond lengths and Bader charges are used to explore the electronic properties and chemical bonding of the O-rich compounds. The Na-rich compounds stabilized at extreme pressures (P > 200 GPa) are electrides with strong interstitial electron localization. The C2/c phase of Na(3)O is found to be a zero-dimensional electride with an insulating character. The Cmca phase of Na(4)O is a one-dimensional metallic electride. These findings of new compounds with unusual chemistry might stimulate future experimental and theoretical investigations.