Details

Autor(en) / Beteiligte

• Klein, Benedikt P.
• van der Heijden, Nadine J.
• Kachel, Stefan R.
• Franke, Markus
• Krug, Claudio K.
• Greulich, Katharina K.
• Ruppenthal, Lukas
• Müller, Philipp
• Rosenow, Phil
• Parhizkar, Shayan
• Bocquet, François C.
• Schmid, Martin
• Hieringer, Wolfgang
• Maurer, Reinhard J.
• Tonner, Ralf
• Kumpf, Christian
• Swart, Ingmar
• Gottfried, J. Michael

Titel

Molecular Topology and the Surface Chemical Bond: Alternant Versus Nonalternant Aromatic Systems as Functional Structural Elements

Ist Teil von

• Physical review. X, 2019-02, Vol.9 (1), p.011030, Article 011030

Ort / Verlag

College Park: American Physical Society

Erscheinungsjahr

2019

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The interaction of carbon-based aromatic molecules and nanostructures with metals can strongly depend on the topology of theirπ-electron systems. This is shown with a model system using the isomers azulene, which has a nonalternantπsystem with a 5-7 ring structure, and naphthalene, which has an alternantπsystem with a 6-6 ring structure. We found that azulene can interact much more strongly with metal surfaces. On copper (111), its zero-coverage desorption energy is 1.86 eV, compared to 1.07 eV for naphthalene. The different bond strengths are reflected in the adsorption heights, which are 2.30 Å for azulene and 3.04 Å for naphthalene, as measured by the normal incidence x-ray standing wave technique. These differences in the surface chemical bond are related to the electronic structure of the molecularπsystems. Azulene has a low-lying LUMO that is close to the Fermi energy of Cu and strongly hybridizes with electronic states of the surface, as is shown by photoemission, near-edge x-ray absorption fine-structure, and scanning tunneling microscopy data in combination with theoretical analysis. According to density functional theory calculations, electron donation from the surface into the molecular LUMO leads to negative charging and deformation of the adsorbed azulene. Noncontact atomic force microscopy confirms the deformation, while Kelvin probe force microscopy maps show that adsorbed azulene partially retains its in-plane dipole. In contrast, naphthalene experiences only minor adsorption-induced changes of its electronic and geometric structure. Our results indicate that the electronic properties of metal-organic interfaces, as they occur in organic (opto)electronic devices, can be tuned through modifications of theπtopology of the molecular organic semiconductor, especially by introducing 5-7 ring pairs as functional structural elements.