title: DFT study of the chlorine promotion effect on the ethylene adsorption over iron clusters.
abstract: This work explores how electronic perturbations induced by chlorine atoms can enhance the activity of iron toward ethylene. The metal clusters include Fen (n=2-4), in which each adatom (Cl) has an inclination to be adsorbed at the bridge site with electrostatic interaction. Ethylene adsorption over pure and chlorine-doped FenClm (n,m≤4) clusters is analyzed using density functional theory (DFT) calculations, in π and di-σ adsorption modes. One of the interesting features is that the adsorption mode of ethylene changes by going from trimers to tetramers. Ethylene never orients toward di-σ mode for FeFe bond in Fe2 and Fe3 series, while this orientation is preferred in tetramers. Our results demonstrate that the progressive change in the ethylene adsorption could not be sustained with increasing portion of chlorine in metal cluster. In this study, we attempt to provide a sensible justification for this phenomenon by the natural bond orbital (NBO) and quantum theory of atoms-in-molecules (QTAIM) analyses.
authors.affiliation: Chemistry Department, College of Science, Shiraz University, 7146713565 Shiraz Iran. Electronic address: farideh.pahlavan64@ymail.com.
authors.forename: Farideh
authors.initials: F
authors.lastname: Pahlavan
authors.affiliation: Chemistry Department, College of Science, Shiraz University, 7146713565 Shiraz Iran. Electronic address: pakiariah@gmail.com.
authors.forename: Ali H
authors.initials: AH
authors.lastname: Pakiari
mesh_terms: D002713:Chlorine / Q000737:chemistry*; D005030:Ethylenes / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D007501:Iron / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D011789:Quantum Theory
chemical_list: D005030:Ethylenes; D007477:Ions; D002713:Chlorine; C036216:ethylene; D007501:Iron
keywords: Atoms in molecules (AIM); Chlorine promotion effect; Chlorine-doped iron cluster; Iron interacting systems; Natural bond orbital (NBO)