Atomic structures of benzene and pyridine on Si(5512)-2 x 1

The adsorption structures of benzene and pyridine on Si(5 5 12)-2 x 1 were studied at 80 K by using a low-temperature scanning tunneling microscope and density functional theory calculations. These structures are different from those observed on low-index Si surfaces: benzene molecules exclusively bind to two adatoms, that is, with di-sigma bonds between carbon atoms and silicon adatoms, leading to the loss of benzene aromaticity; in contrast, pyridine molecules interact with adatom(s) through either Si-N dative bonding or di-sigma bonds. Dative bonding configurations with pyridine aromaticity are the dominant adsorption features and are more stable than di-sigma bonding configurations. Thus the dative bonding of nitrogen-containing heteroaromatic molecules provides a strategy for the controlled attachment of aromatic molecules to high-index surfaces.