HREELS study of the adsorption mechanism and orientational order of 2-mercaptobenzoxazole on Cu(1 0 0)

Organic molecules with sulfur-containing headgroups interacting with noble metal surfaces represent a fruitful class of systems with potential relevance in new device technology. Within this context, the room temperature adsorption of 2-mercaptobenzoxazole (MBO) on the Cu(1 0 0) surface has been studied by high-resolution electron energy-loss spectroscopy (HREELS) as a function of molecular exposure. At low coverage, the HREEL spectra present only one mode at 93 meV (750 cm−1), which is attributed to the out-of-plane C–H bending γCH. Its off-specular angular dependence indicates that the molecules lie almost flat on the surface. At higher coverage, the MBO layer orders in a p(2 × 2) superstructure, and energy loss peaks at higher energies appear. These features can be assigned to in-plane vibrations indicating that the molecular axis tilts toward a more vertical position, thus allowing a closer molecular packing. Assignment of the HREELS peaks is confirmed by estimation of the gas phase normal modes of the free molecule, evaluated by ab initio methods. The absence of the N–H stretching mode in the HREEL spectra indicates that the H atom bonded to nitrogen in the gas-phase molecule is lost upon adsorption, suggesting that MBO molecule adsorbs on the Cu surface as a thiolate.