Many-electron calculations of the phase stability of ZrO₂ polymorphs

Abstract

Zirconia (ZrO2) has been well studied experimentally for decades, but still poses a severe challenge for computational approaches. We present thorough many-electron benchmark calculations within the random-phase approximation framework of the phase stabilities of the most common ZrO2 phases and assess the performance of various density functional theory (DFT) and beyond-DFT methods. We find that the commonly used DFT and hybrid functionals strongly overestimate both the energetic differences of the common phases and the stability of two metastable phases. The many-electron calculations offer a significantly improved description of the predicted bulk properties, especially of the bulk modulus B0. On the DFT level, the van der Waals corrected meta-generalized-gradient approximation (SCAN-rVV10) provides much better agreement with the experimental values than other (semi)local and hybrid approaches.