Stability and Metastability of Clusters in a Reactive Atmosphere: Theoretical Evidence for Unexpected Stoichiometries of MgMOx

By applying a genetic algorithm and ab initio atomistic thermodynamics, we identify the stable and metastable compositions and structures of MgMOx clusters at realistic temperatures and oxygen pressures. We find that small clusters (M less than or similar to 5) are in thermodynamic equilibrium when x > M. The nonstoichiometric clusters exhibit peculiar magnetic behavior, suggesting the possibility of tuning magnetic properties by changing environmental pressure and temperature conditions. Furthermore, we show that density-functional theory with a hybrid exchange-correlation functional is needed for predicting accurate phase diagrams of metal-oxide clusters. Neither a (sophisticated) force field nor density-functional theory with (semi) local exchange-correlation functionals is sufficient for even a qualitative prediction.