title: Modeling adsorbate-induced property changes of carbon nanotubes.
abstract: Because of their potential for chemical functionalization, carbon nanotubes (CNTs) are promising candidates for the development of devices such as nanoscale sensors or transistors with novel gating mechanisms. However, the mechanisms underlying the property changes due to functionalization of CNTs still remain subject to debate. Our goal is to reliably model one possible mechanism for such chemical gating: adsorption directly on the nanotubes. Within a Kohn-Sham density functional theory framework, such systems would ideally be described using periodic boundary conditions. Truncating the tube and saturating the edges in practice often offers a broader selection of approximate exchange-correlation functionals and analysis methods. By comparing the two approaches systematically for NH3and NO2adsorbates on semiconducting and metallic CNTs, we find that while structural properties are less sensitive to the details of the model, local properties of the adsorbate may be as sensitive to truncation as they are to the choice of exchange-correlation functional, and are similarly challenging to compute as adsorption energies. This suggests that these adsorbate effects are nonlocal. © 2017 Wiley Periodicals, Inc.
authors.affiliation: Department of Chemistry, Institute for Inorganic and Applied Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, Hamburg, 20146, Germany.
authors.forename: Lynn
authors.initials: L
authors.lastname: Groß
authors.affiliation: Department of Chemistry, Institute for Inorganic and Applied Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, Hamburg, 20146, Germany.
authors.forename: Marc Philipp
authors.initials: MP
authors.lastname: Bahlke
authors.affiliation: Department of Chemistry, Institute for Inorganic and Applied Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, Hamburg, 20146, Germany.
authors.forename: Torben
authors.initials: T
authors.lastname: Steenbock
authors.affiliation: Department of Chemistry, Institute for Physical Chemistry, University of Hamburg, Grindelallee 117, Hamburg, 20146, Germany.
authors.forename: Christian
authors.initials: C
authors.lastname: Klinke
authors.affiliation: Department of Chemistry, Institute for Inorganic and Applied Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, Hamburg, 20146, Germany.
authors.forename: Carmen
authors.identifier: 0000-0002-9496-0664
authors.initials: C
authors.lastname: Herrmann
keywords: carbon nanotubes; density functional theory; local properties; noncovalent functionalization