Nanosystem’s density functional theory study of the chlorine adsorption on the Fe(100) surface

Abstract This contribution investigates chlorine (Cl) interaction with the Fe(100) surface, with a focus on governing adsorption energies and geometrical features at the nanoscale using the density functional theory (DFT) approach. The Cl/Fe(100) system can be considered as a building block to create nanosystems with specific and desired electronic, material, mechanical, or environmental properties. We report adsorption energies, surface relaxations. and buckling distances for Cl adsorbed as a function of Cl coverage. The computational DFT framework employs a vdW-DF functional with coverages varying from 0.25 to 1 ML. Adsorption at a bridge site with coverage of 0.5 ML appears to be the most preferred site, with an adsorption energy of −4.44 eV. For all coverages, Cl adsorption at the bridge and hollow sites incurs slightly higher adsorption energies than adsorption at the top (T) site. The potential energy surface (PES) for the dissociation of a Cl molecule over the Fe(100) surface was calculated. Dissociative adsorption of the Cl molecule on Fe(100) ensues via a modest activation barrier of only 0.58 eV in a noticeably exothermic reaction of 2.94 eV. In agreement with experimental observations, the work function decreases upon Cl addition in reference to the clean iron surface. The electronic interaction between Cl and the Fe(100) surface was examined by calculating the differential charge density distribution of the most stable structure (B-0.5 ML). The vdW-DF interactions increase the adsorption energies and reduce the equilibrium distances when compared with the corresponding results from plain DFT.