Surface magnetism in O2 dissociation—from basics to application

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First-principles calculations were performed to investigate magnetic phenomena in surface reactions involving O2. We present two magnetized surface cases: (1) oxidation of paramagnetic Ag, and magnetic properties of the high coverage oxide phase, which correspond to a magnetic impurity superlattice on paramagnetic surfaces and (2) oxidation of ferromagnetic Pt, represented by the Pt layer on M (M = Fe and Co) relevant to the oxidation reduction reaction (ORR) on Pt, in relation to both fundamental and application interests. In the first case, we found that the dissociative adsorption of O2, resulting in oxide phases in Ag(111), reveals interesting magnetic interactions. We note that the magnetic states are induced by the ferromagnetic superexchange interactions and Ruderman–Kittel–Kasuya–Yosida (RKKY) interactions. Specifically, the superlattice structures with short O–O distances have an effective ferromagnetic superexchange and RKKY interaction. In the second case, we found that a magnetic moment is induced on the Pt layer by the M substrate. The spin polarization of Pt-d states is due to hybridization with M-d states. The d-band center (εd) of Pt (on M), is shifted downwards with respect to pure Pt. However, because of the spin polarization, the otherwise filled spin-down dzz orbital in paramagnetic pure Pt is shifted towards the Fermi level. This promotes πz↑–dzz↓ interactions, which influences the O2–Pt interaction at O2 far from the surface. Details and mechanisms of these two magnetic phenomena are discussed.