Fluorine adsorption on transition metal surfaces - A DFT study

Abstract

Based on density functional theory calculations, the adsorption of fluorine was investigated on a) Cu(111), Au(111), Pd(111) and Pt(111) surfaces, b) on Pd monolayer surfaces over Cu(111), Au(111) and Pt(111) surfaces and c) on the surfaces of Pd(111) monocrystals with an inserted metal monolayer (M = Cu, Au or Pt) underneath the first Pd surface layer. The results evidenced that the adsorption did not cause significant changes of the structural parameters of metallic substrate. The strongest adsorption, amounting to -4.49 eV, was calculated in the case of the Cu(111) surface. The Cu(111) and Au(111) surface atoms interact with F adatoms exclusively by the mediation of the sp-band, while the surface atoms of Pt and Pd-based surfaces interact with F adatoms additionally by the mediation of the d-band. In the case of Pt(111) and PdML/M(111) surfaces, the binding energies correlated with the d-band center positions, which indicated a significant contribution of covalent interaction. These results confirmed that the nature of surface interaction of highly electronegative F atom with metallic surfaces depends significantly on the nature of the metal substrate. ©2013 SCS.