Correct and Accurate Polymorphic Energy Ordering of Transition-Metal Monoxides Obtained from Semilocal and Onsite-Hybrid Exchange-Correlation Approximations

The relative energetic stability of the structural phases of common antiferromagnetic transition-metal oxides (MnO, FeO, CoO, and NiO) within the semilocal and hybrid density functionals are fraught with difficulties. In particular, MnO is known to be the most difficult case for almost all common semilocal and hybrid density approximations. Here, we show that the meta-generalized gradient approximation (meta-GGA) constructed from the cuspless hydrogen model and Pauli kinetic energy density (MGGAC) can lead to the correct phase as the ground-state of MnO. The relative energy differences of zinc blende (zb) and rock salt (rs) structures as computed using MGGAC are found to be in nice agreement with those obtained from high-level correlation methods like the random phase approximation or quantum Monte Carlo techniques. Besides, we have also applied the onsite hybrid functionals (closely related to DFT+U) based on GGA and meta-GGA functionals, and it is shown that a relatively high amount of Hartree-Fock exchange is necessary to obtain rs as the ground-state phase. Our present investigation suggests the semilocal MGGAC and onsite hybrids, both being computationally cheap, as methods of choice for the calculation of the relative stability of antiferromagnetic transition-metal oxides having potential applications in solid-state physics and structural chemistry. © 2022 American Chemical Society.