Challenges in the use of density functional theory to examine catalysis by M-doped ceria surfaces

For CeO₂ or M-doped CeO₂ catalysts, reliable energetics associated with surface reactivity requires accurate representation of oxidized and reduced metal states. Density functional theory (DFT) is used extensively for metals and metal oxides; however, for strongly correlated electron materials, conventional DFT fails to predict both qualitative and quantitative properties. This is the result of a localized electron self-interaction error that is inherit to DFT. DFT+U has shown promise in correcting energetic errors due to the self-interaction error, however, its transferability across processes relevant to surface catalysis remains unclear. Hybrid functionals, such as HSE06, can also be used to correct this self-interaction error. These hybrid functionals are computationally intensive, and especially demanding for periodic surface slab models. This perspective details the challenges in representing the energetics of M-doped ceria catalyzed processes and examines using DFT extensions to model the localized electronic properties.