Nonadditivity of the adsorption energies of linear acenes on au(111): Molecular anisotropy and many-body effects

Adsorption energies of chemisorbed molecules on inorganic solids usually scale linearly with molecular size and are well described by additive scaling laws. However, much less is known about scaling laws for physisorbed molecules. Our temperature-programmed desorption experiments demonstrate that th...

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Hauptverfasser: Maaß, Friedrich (VerfasserIn) , Ajdari, Mohsen (VerfasserIn) , Tegeder, Petra (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: February 15, 2019
In: The journal of physical chemistry letters
Year: 2019, Jahrgang: 10, Heft: 5, Pages: 1000-1004
ISSN:1948-7185
DOI:10.1021/acs.jpclett.9b00265
Online-Zugang:Verlag, Volltext: https://doi.org/10.1021/acs.jpclett.9b00265
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Verfasserangaben:Friedrich Maass, Mohsen Ajdari, Fairoja Cheenicode Kabeer, Maximilian Vogtland, Alexandre Tkatchenko, and Petra Tegeder
Beschreibung
Zusammenfassung:Adsorption energies of chemisorbed molecules on inorganic solids usually scale linearly with molecular size and are well described by additive scaling laws. However, much less is known about scaling laws for physisorbed molecules. Our temperature-programmed desorption experiments demonstrate that the adsorption energy of acenes (benzene to pentacene) on the Au(111) surface in the limit of low coverage is highly nonadditive with respect to the molecular size. For pentacene, the deviation from an additive scaling of the adsorption energy amounts to as much as 0.7 eV. Our first-principles calculations explain the observed nonadditive behavior in terms of anisotropy of molecular polarization stemming from many-body electronic correlations. The observed nonadditivity of the adsorption energy has implications for surface-mediated intermolecular interactions and the ensuing on-surface self-assembly. Thus, future coverage-dependent studies should aim to gain insights into the impact of these complex interactions on the self-assembly of π-conjugated organic molecules on metal surfaces.
Beschreibung:Gesehen am 29.04.2019
Beschreibung:Online Resource
ISSN:1948-7185
DOI:10.1021/acs.jpclett.9b00265