Li-doped MgO is a potential catalyst for the oxidative coupling of methane, whereby surface Li+ O- centers are suggested to be the chemically active species. To elucidate the role of Li in the MgO matrix, two model systems are prepared and their morphological, optical and magnetic properties as a function of Li doping are investigated. The first is an MgO film deposited on Mo(001) and doped with various amounts of Li, whereas the second is a powder sample fabricated by calcination of Li and Mg precursors in an oxygen atmosphere. Scanning tunneling and transmission electron microscopy are performed to characterize the morphology of both samples. At temperatures above 700 K, Li starts segregating towards the surface and forms irregular Li-rich oxide patches. Above 1050 K, Li desorbs from the MgO surface, leaving behind a characteristic defect pattern. Traces of Li also dissolve into the MgO, as concluded from a distinct optical signature that is absent in the pristine oxide. No electron paramagnetic resonance signal that would be compatible with Li+O- centers is detected in the two Li/MgO samples. Density-functional theory calculations are used to determine the thermodynamic stability of various Li-induced defects in the MgO. The calculations clarify the driving forces for Li segregation towards the MgO surface, but also rationalize the absence of Li+O- centers. From the combination of experimental and theoretical results, a detailed picture arises on the role of Li for the MgO properties, which can be used as a starting point to analyze the chemical behavior of the doped oxide in future

The CO binding behavior to gold particles supported on MgO thin films has been analyzed with scanning tunneling microscopy (STM) and infrared spectroscopy (IRAS). The ad-particles accommodate excess electrons that originate either from a charge transfer through the thin oxide film or from a local interaction with electron-rich oxide defects that act as Au nucleation centers. The enhanced electron density in the Au aggregates affects both the spatial distribution and the vibrational properties of adsorbed CO species. Whereas preferential CO attachment to the chemically unsaturated and electron-rich boundary sites of the Au islands is deduced from the STM data, a continuous downshift of the CO stretching frequency with decreasing particle size is observed in IRAS. Both results are interpreted in the light of CO adsorption to negatively charged metal aggregates and used to draw general conclusions on the interplay between charge and adsorption properties of confined metal systems.

Misfit dislocations in a thin MgO/Mo͑001͒ film have been investigated by conductance and light-emission spectroscopy using scanning tunneling microscopy and electron-paramagnetic resonance ͑EPR͒ spectroscopy. The line defects exhibit a higher work function than the pristine MgO, being explained by their ability to trap electrons. The electron traps are associated with a nonstoichiometric defect composition in thin oxide films and attractive pockets in the Madelung potential in thicker ones. The latter traps can be reproducibly filled by the adsorption of atomic hydrogen, which gives rise to a free-electronlike signal in EPR spectroscopy.