title: Ozonolysis of diamond.
abstract: The oxidation of diamond is attracting increasing interest, in the light of efforts to modulate its electronic properties for device applications. Ozone is a promising candidate oxidant species, allowing low temperature processing compared with molecular dioxygen. Here, we present first-principles molecular dynamics simulations for the dissociative adsorption of ozone on the {001} surface of diamond, carried out at the level of density functional theory. We find that ozone readily oxidizes the surface, with two distinct modes of reaction: partial dissociation results in deposition of a single oxygen adatom in an alkoxide-like structure that rapidly converts to an epoxide-like configuration; complete dissociation results in two adatoms located in ketone-like structures, with a third occupying an alkoxide geometry, expected to revert to the epoxide in due course. We describe not only the structural changes during the reactions, but also the variations in electron and spin densities that reveal the bonding rearrangements.
authors.affiliation: Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, UK.
authors.forename: Christian K
authors.initials: CK
authors.lastname: Fink
authors.forename: Stephen J
authors.initials: SJ
authors.lastname: Jenkins