The results of spin-polarized density functional theory calculations for O
2 dissociative adsorption on Pt monolayer on Fe(001) (Pt
ML/Fe(001)) structure are presented and are compared with that of Pt(001). The potential energy curves for the reaction of Pt with O
2 as a function of O
2 center-of-mass distance from the platinum layer and O-O interatomic distance show that Pt
ML/Fe(001) produces a combination of lower activation barrier for O
2 dissociation and weaker O-atom binding which are both beneficial for a easier O
2 dissociation to produce adsorbed O and for subsequent reactions of O with other surface species for O
2 reduction process. Local density of states at Pt surface shows induced spin polarization on the Pt atomic layer characterized by d
zz peak at the Fermi level, in good agreement with experimental findings. Such effect increases unfilled d
zz orbital on Pt surface modifying Pt electronic surface structure towards a favorable O
2-Pt d interaction. Decrease in the magnetic moments of O and Pt atoms upon O adsorption indicates an antiparallel O unpaired electron spin alignment with Pt spin rendering consequent stabilization and a lowering of energy cost to O
2 activation. On the other hand, the weaker O binding reflects the stronger Pt-Fe interlayer bonding typical for such bimetallic systems. [DOI: 10.1380/ejssnt.2007.117]
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