Interaction of Gold with a Pinwheel TiO∼1.2 Film Formed on Rh(111) Facet: STM and DFT Studies

The atomic structure of “pinwheel” TiO∼1.2 ultrathin oxide (w-TiO-UTO) layer and its reaction with gold are studied by scanning tunneling microscopy (STM) imaging and density functional theory (DFT) calculations. The UTO film was formed as an encapsulation layer on the top facet (111) of stripe-like Rh nanoparticles supported on a TiO2(110) substrate. For proposing a structural model, the previous STM, photoelectron (XPS), and ion scattering spectroscopy (LEIS) results were also taken into account. DFT calculations were carried out within the generalized gradient approximation (GGA-PBE) in the frame of the Quantum Espresso code. A Rh(111) slab of four layers with a TiO1.14 overlayer and a Rh–Ti–O stacking sequence were used. In the starting model, the ratio between hcp and fcc sites filled with Ti atoms was 1.54 (the same value for O atoms was 2.2) on the top of Rh layers. The simulation of the STM images of the relaxed structure was done following the Tersoff–Hamann approximation. The main structural cha...