EPR properties of Au atoms adsorbed on various sites of the MgO(1 0 0) surface from relativistic DFT calculations

Abstract Using all electron fully relativistic DFT calculations we have computed the EPR properties of Au atoms bound to various sites of the MgO surface. Changes in g-tensor and hyperfine coupling constants provide a way to identify the gold adsorption site and to map the surface morphology by comparison of measured and calculated EPR spectra. We found a strong reduction of the isotropic hyperfine coupling constant, a iso (Au), for adsorbed gold compared to the free atom; this reduction, which is about 45% for terrace sites, is more pronounced when Au interacts with low-coordinated sites like steps, edges and corners where it is about 60%. The reduction of a iso (Au) is accompanied by a corresponding increase of the superhyperfine interaction with the surface oxygen sites, as measured by a iso ( 17 O). Large anisotropies in the g-tensor are computed for all sites