Kinetics of Oxygen Surface Exchange on Epitaxial Ruddlesden-Popper Phases and Correlations to First-Principles Descriptors

Through alignment of theoretical modeling with experimental measurements of oxygen surface exchange kinetics on (001)-oriented La_2-xSr_xMO_4+δ (M = Co, Ni, Cu) thin films, we demonstrate here the capability of the theoretical bulk O 2p-band centers to correlate with oxygen surface-exchange kinetics of the Ruddlesden-Popper oxide (RP₂₁₄) (001)-oriented thin films. In addition, we demonstrate that the bulk O 2p-band centers can also correlate with the experimental activation energies for bulk oxygen transport and oxygen surface exchange of both the RP₂₁₄ and the perovskite polycrystalline materials reported in the literature, indicating the effectiveness of the bulk O 2p-band centers in describing the associated energetics and kinetics. We propose that the opposite slopes of the bulk O 2p-band center correlations between the RP₂₁₄ and the perovskite materials are due to the intrinsic mechanistic differences of their oxygen surface exchange kinetics and bulk anionic transport.