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

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Abstract: We report a combined experimental and theoretical study of the candidate type-II Weyl semimetal MoTe2. Using laser-based angle-resolved photoemission, we resolve multiple distinct Fermi arcs on the inequivalent top and bottom (001) surfaces. All surface states observed experimentally are reproduced by an electronic structure calculation for the experimental crystal structure that predicts a topological Weyl semimetal state with eight type-II Weyl points. We further use systematic electronic structure calculations simulating different Weyl point arrangements to discuss the robustness of the identified Weyl semimetal state and the topological character of Fermi arcs in MoTe2.