Phase stability of entropy stabilized oxides with the α-PbO2 structure

Abstract The prediction of new high entropy oxides (HEOs) remains a profound challenge due to their inherent chemical complexity. In this work, we combine experimental and computational methods to search for new HEOs in the tetravalent A O 2 family, using exclusively d 0 and d 10 cations. Our aim is to explain the phase stability of the α -PbO 2 structure, which is found for the medium entropy oxide (Ti, Zr, Hf, Sn)O 2 . Using a pairwise approach to approximate the mixing enthalpy, we confirm that α -PbO 2 is the expected lowest energy structure for this material above other candidates including rutile, baddeleyite, and fluorite structures. We also show that no other five-component compound composed of the tetravalent cations considered here is expected to form under solid state synthesis conditions, which we verify experimentally. Ultimately, we conclude that the flexible geometry of the α -PbO 2 structure can be used to understand its stability among tetravalent HEOs.