Screened Hybrid Exact Exchange Correction Scheme for Adsorption Energies on Perovskite Oxides

Abstract

The bond formation between an oxide surface and oxygen, which is of importance for numerous surface reactions including catalytic reactions, is investigated within the framework of hybrid density functional theory that includes nonlocal Fock exchange. We show that there exists a linear correlation between the adsorption energies of oxygen on LaMO 3 (M = Sc-Cu) surfaces obtained using a hybrid functional (e.g., Heyd-Scuseria-Ernzerhof) and those obtained using a semilocal density functional (e.g., Perdew-Burke-Ernzerhof) through the magnetic properties of the bulk phase as determined with a hybrid functional. The energetics of the spin-polarized surfaces follows the same trend as corresponding bulk systems, which can be treated at a much lower computational cost. The difference in adsorption energy due to magnetism is linearly correlated to the magnetization energy of bulk, that is, the energy difference between the spin-polarized and the non-spin-polarized solutions. Hence, one can estimate the correction to the adsorption energy as obtained from a semilocal functional directly from the bulk magnetization energy from a hybrid functional.