Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 14, Issue 2, Pages 691-696Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c1cp22875g
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Funding
- Deutsche Forschungsgemeinschaft (DFG) [SPP 1355]
- collaborative research center [SFB 658]
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The adsorption behavior of alpha-octithiophene (8T) on the Au(111) surface as a function of 8T coverage has been studied with low-temperature scanning tunneling microscopy, high resolution electron energy loss spectroscopy as well as with angle-resolved two-photon photoemission and ultraviolet photoemission spectroscopy. In the sub-monolayer regime 8T adopts a flat-lying adsorption geometry. Upon reaching the monolayer coverage the orientation of 8T molecules changes towards a tilted configuration, with the long molecular axis parallel to the surface plane, facilitating attractive intermolecular pi-pi-interactions. The photoemission intensity from the highest occupied molecular orbitals (HOMO and HOMO - 1) possesses a strong dependence on the adsorption geometry due to the direction of the involved transition dipole moment for the respective photoemission process. The change in molecular orientation as a function of coverage in the first molecular layer mirrors the delicate balance between intermolecular and molecule/substrate interactions. Fine tuning of these interactions opens up the possibility to control the molecular structure and accordingly the desirable functionality.
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