Interaction of Water with the CaO(001) Surface

The interaction of water with the CaO(001) surface has been studied from ultrahigh-vacuum to submillibar water vapor pressures and at temperatures of 100 and 300 K using well-structured CaO(001)/Mo(001) thin-film model systems. Infrared reflection absorption spectroscopy (IRAS), X-ray photoelectron spectroscopy (XPS), and scanning tunneling microscopy (STM) in combination with density functional theory (DFT) calculations have been employed to reveal the correlation between the vibrational frequencies of the hydroxyl groups and the distinct hydroxylated surface phases that develop as a function of water exposure. In the low-coverage regime, water monomers, small water clusters, and one-dimensional water chains are formed on the CaO(001) surface. At increasing water coverages, water-induced structural disorder is observed, indicating partial solvation of Ca2+ ions. Partial transformation of CaO(001) into a Ca(OH)2-like phase occurs upon dosing of water at submillibar water pressure. In addition, it was found that interfacial hydroxyl groups formed on the CaO(001) surface during water exposure at temperatures as low as 100 K shift the temperatures for ice desorption and for the transition from amorphous solid water to crystalline ice by 10 K as compared to those for the nonhydroxylated MgO surface.