Fluorine adsorption on transition metal surfaces: A DFT study

Abstract

On the basis of Density Functional Theory calculation, 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) surface, and c) on the surfaces of Pd(111) monocrystal with inserted metal monolayer (M = Cu, Au, Pt) underneath the first Pd surface layer. The results evidenced that the adsorption did not cause significant structural parameters of metallic substrate. The strongest adsorption amounting to -4.49 eV was calculated in the case of Cu(111) surface. The Cu(111) and Au(111) surface atoms interact with F adatoms by the mediation of sp-band exclusively, while the surface atoms of Pt and Pd-based surfaces interact with F adatoms additionally by the mediation of d-band, too. In the case of Pt(111) and PdML/M(111) surfaces, the binding energies are 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.