Energy level alignment of cyclohexane on Rh(111) surfaces: The importance of interfacial dipole and final-state screening

Adsorption states and electronic structure of cyclohexane on clean and hydrogen-saturated Rh(111) surfaces were investigated by scanning tunneling microscopy and photoelectron spectroscopy. Monolayer cyclohexane molecules form an ordered superstructure on the clean Rh(111) surface. The energy level alignment of adsorbed cyclohexane depends on each adsorption site; molecular orbitals of adsorbed cyclohexane on the atop site have lower binding energies than those on the other sites. In contrast, it becomes insensitive to adsorption sites on the hydrogen-saturated Rh(111) surface. By preadsorption of hydrogen, all cyclohexane molecular orbitals are uniformly shifted to lower binding energy compared to those on the clean Rh(111) surface. The observed energy level alignment of cyclohexane on the Rh(111) surfaces is determined by the vacuum level shift and the final-state screening effects. (C) 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4775842]