In this work we combine scanning tunneling microscopy, near-edge X-ray absorption fine structure spectroscopy, X-ray photoemission spectroscopy and density functional theory to resolve a long-standing confusion regarding the adsorption behaviour of benzonitrile on Si(001) at room temperature. We find that a trough-bridging structure is sufficient to explain adsorption at low coverages. At higher coverages when steric hindrance prevents the phenyl ring lying flat on the surface, the 2+2 cycloaddition structure dominates.
O’Donnell, K. M., Hedgeland, H., Moore, G., Suleman, A., Siegl, M., Thomsen, L., … Schofield, S. R. (2016). Orientation and stability of a bi-functional aromatic organic molecular adsorbate on silicon. Physical Chemistry Chemical Physics, 18(39), 27290–27299. https://doi.org/10.1039/c6cp04328c