Theoretical study of NH3 adsorption on Fe(110) and Fe(111) surfaces

With the aim of understanding the nature of the interactions between organic molecules and metal surfaces, the adsorption of NH3 onto model Fe(110) and Fe(111) surfaces has been studied with use of the molecular orbital and density functional theories. B3LYP calculations have revealed that the on-top site is most suitable for adsorption of NH3 both on Fe(110) and on Fe(111). Mulliken population analysis in terms of the MO's of the two fragment systems suggested that electron delocalization from NH3 to the Fe surface should play a key role in the adsorption. Then, our transformation scheme of fragment orbitals has demonstrated that the electron delocalization is represented well only by a pair of interaction orbitals. The NH3 molecule provides the occupied interaction orbital bearing a close resemblance to the highest occupied (HO) MO, whereas the Fe surface prepares the paired unoccupied orbital that is localized at the adsorption site and overlaps in-phase with the orbital of NH3. Not only the lowest unoccupied (LU) MO but also other unoccupied MO's have been shown to participate significantly in the interaction. The reason the on-top site is the most preferable position for NH3 attack has been elucidated by investigating the interaction orbitals.