title: Topological study of intramolecular hydrogen bonding in beta-hydroxyethylperoxy radical and beta-hydroxyethoxy radical along its dissociation pathway.
abstract: The presence of intramolecular hydrogen bond (IHB) in beta-hydroxyethylperoxy and beta-hydroxyethoxy radicals was investigated using the QTAIM topological study on UB3LYP/6-311++G(2d,2p) charge densities. Only one of the two conformers of beta-hydroxyethylperoxy radical which were previously considered to present IHB displays a bond critical point (BCP) associated to an IHB. Furthermore, the atomic energies and electron populations indicate no evidence of IHB in the second conformer. Nevertheless, very small differences in molecular energies were obtained using several one-step and multi-step methods (G3, G3B3) between both conformers. No BCP is found between the hydroxyl hydrogen and the oxygen in the most stable conformer or in the transition state for the dissociation path of beta-hydroxyethoxy radical. However, a BCP is formed in the last steps of this path, thereby yielding H-bonded products.
authors.affiliation: Department of Chemistry, University of Antwerp, Universiteitplein 1, B-2610, Antwerpen, Belgium.
authors.forename: Marcos
authors.initials: M
authors.lastname: Mandado
authors.forename: Ricardo A
authors.initials: RA
authors.lastname: Mosquera
authors.forename: Christian
authors.initials: C
authors.lastname: Van Alsenoy
mesh_terms: D005026:Ethylene Glycols / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry* / Q000378:metabolism*; D006860:Hydrogen Bonding; D008958:Models, Molecular; D013499:Surface Properties
chemical_list: D005026:Ethylene Glycols; D005609:Free Radicals; D006859:Hydrogen