A novel mechanism of spin-orientation dependence of O2 reactivity from first principles methodsElectronic supplementary information (ESI) available. See DOI: 10.1039/c6cy01198e

A new mechanism beyond charge transfer, spin-orientation dependence of O 2 reactivity on a ferromagnetic surface, is presented using first-principles methods. O 2 favors the anti-parallel configuration at the transition state and a parallel configuration at distances above and below it. This suggests coupling and is found to originate from the unquenched spin moment of O 2 . A novel mechanism of oxygen reaction on a metal surface beyond the present charge transfer or hybridization mechanism, spin-orientation dependence via a coupling mechanism due to the finite spin moment of O 2 at the transition state, is obtained using a combination of spin density functional theory (SDFT) and constrained DFT.