Evaluation for the configurational and electronic state of SO3 adsorbed on Pt surface

Abstract We evaluate the adsorption of SO 3 molecule on the Pt (1 1 1) surface using the first-principles calculations by a slab model with a periodic boundary condition. We find that there are four stable adsorption configurations on the Pt surface, where SO 3 molecules are adsorbed above the three-fold fcc and hcp sites. In two of these configurations, S and two O atoms are bound to the Pt atoms, and in two other of them, all the three O atoms are bound to Pt surface atoms. Besides, it is found that molecular orbitals of SO 3 and those of Pt surface are hybridized in the active metal d-bands region, that the localized molecular orbitals in SO 3 are stabilized, and that the charge is transferred from Pt to S 3p by SO 3 adsorption on Pt surface though the other interaction of S and O (bound to Pt) component with Pt is little. In addition, the bond between S and O bound to Pt become weak by SO 3 adsorption on Pt surface because the charge polarization to O–Pt bond weakens the bond between S and O bound to Pt. This interaction is assumed to encourage the breakage of S–O bond.