title: Disintegration and field evaporation of thiolate polymers in high electric fields.
abstract: High electrostatic fields cause major changes in polymers, structural (e.g. electrostriction) and electronic (e.g. reduction of the "band gap" with final metallization). Using density functional theory we have studied field effects on amino-alkane-thiols and perfluoro-alkane-thiols adsorbed on a metal substrate. Our results agree well with the APT fragmentation spectra obtained by Stoffers, Oberdorfer and Schmitz and shed light on disintegration pathways. We demonstrate that in SAMs the HOMO/LUMO gap is again reduced as a function of the field strength and vanishes at evaporation. We also follow the field dependence of the dielectric constant and polarizability.
authors.affiliation: Department of Physics and Atmospheric Science, Dalhousie University, Halifax, Nova Scotia, Canada B3H 3J5. Electronic address: brenden.nickerson@dal.ca.
authors.forename: B S
authors.initials: BS
authors.lastname: Nickerson
authors.affiliation: Department of Physics and Atmospheric Science, Dalhousie University, Halifax, Nova Scotia, Canada B3H 3J5.
authors.forename: M
authors.initials: M
authors.lastname: Karahka
authors.affiliation: Department of Physics and Atmospheric Science, Dalhousie University, Halifax, Nova Scotia, Canada B3H 3J5.
authors.forename: H J
authors.initials: HJ
authors.lastname: Kreuzer
keywords: Atom probe tomography; Field evaporation; Self-assembled monolayers