title: Precursor States of Organic Adsorbates on Semiconductor Surfaces are Chemisorbed and Immobile.
abstract: Intermediate states to covalent attachment of molecules on surfaces, so called precursors, are usually considered to be physisorbed and mobile. We show that this view should be reconsidered and provide evidence for a chemisorbed precursor for ethylene on Si(001). The character of the molecule-surface bond as a π complex is determined and quantified using our recently developed method for energy and charge analysis in extended systems. In contrast to previous assumptions, the precursor should thus be immobile, which is underlined by computation of high diffusion energy barriers. This has important implications for understanding and modelling of adsorption kinetics. Our analysis highlights that taking the viewpoint of molecular chemistry helps uncover important aspects in the adsorption process on surfaces. Previous experimental results that appear to be in contrast to our model are examined and reinterpreted.
authors.affiliation: Faculty of Chemistry and Material Sciences Centre, Philipps-Universität Marburg, Hans-Meerwein-Str. 4, 35032, Marburg, Germany.
authors.forename: Josua
authors.identifier: http://orcid.org/0000-0001-7130-0287
authors.initials: J
authors.lastname: Pecher
authors.affiliation: Faculty of Chemistry and Material Sciences Centre, Philipps-Universität Marburg, Hans-Meerwein-Str. 4, 35032, Marburg, Germany.
authors.forename: Ralf
authors.identifier: http://orcid.org/0000-0002-6759-8559
authors.initials: R
authors.lastname: Tonner
keywords: bonding analysis; dative bond; mobility; precursor; surface adsorption