Abstract
A combined study of scanning tunneling microscopy (STM) and density functional theory (DFT) reveals that 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) adsorbs on $\mathrm{Ag}(111)$ at bridge sites in two nonequivalent orientations, one nearly aligned with the $[10\overline{1}]$ substrate axis and the other $18\ifmmode^\circ\else\textdegree\fi{}$ misaligned. Site-specific spectroscopy reveals that molecules in the two configurations exhibit subtle differences in their electronic structure. DFT-based STM simulations trace these back to the influence of distinct local adsorption geometries on the chemical molecule-substrate and molecule-molecule interactions.
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