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

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Details zur Publikation

Autorinnen und Autoren: Klein BP, Van Der Heijden NJ, Kachel SR, Franke M, Krug CK, Greulich KK, Ruppenthal L, Mueller P, Rosenow P, Parhizkar S, Bocquet FC, Schmid M, Hieringer W, Maurer RJ, Tonner R, Kumpf C, Swart I, Gottfried JM
Zeitschrift: Physical Review X
Jahr der Veröffentlichung: 2019
Band: 9
Heftnummer: 1
ISSN: 2160-3308


Abstract

The interaction of carbon-based aromatic molecules and nanostructures with metals can strongly depend on the topology of their pi-electron systems. This is shown with a model system using the isomers azulene, which has a nonalternant pi system with a 5-7 ring structure, and naphthalene, which has an alternant pi system 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 angstrom for azulene and 3.04 angstrom 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 molecular pi systems. 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 the pi topology of the molecular organic semiconductor, especially by introducing 5-7 ring pairs as functional structural elements.


FAU-Autorinnen und Autoren / FAU-Herausgeberinnen und Herausgeber

Hieringer, Wolfgang PD Dr.
Lehrstuhl für Theoretische Chemie


Einrichtungen weiterer Autorinnen und Autoren

Forschungszentrum Jülich GmbH (FZJ)
Philipps-Universität Marburg
Universiteit Utrecht (UU) / Utrecht University
University of Warwick


Zitierweisen

APA:
Klein, B.P., Van Der Heijden, N.J., Kachel, S.R., Franke, M., Krug, C.K., Greulich, K.K.,... Gottfried, J.M. (2019). Molecular Topology and the Surface Chemical Bond: Alternant Versus Nonalternant Aromatic Systems as Functional Structural Elements. Physical Review X, 9(1). https://dx.doi.org/10.1103/PhysRevX.9.011030

MLA:
Klein, Benedikt P., et al. "Molecular Topology and the Surface Chemical Bond: Alternant Versus Nonalternant Aromatic Systems as Functional Structural Elements." Physical Review X 9.1 (2019).

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Zuletzt aktualisiert 2019-21-03 um 09:03