Interplay between adsorbates and polarons: CO on rutile TiO2_2(110)

Polaron formation plays a major role in determining the structural, electrical and chemical properties of ionic crystals. Using a combination of first principles calculations and scanning tunneling microscpoy/atomic force microscopy (STM/AFM), we analyze the interaction of polarons with CO molecules adsorbed on the rutile TiO$_2$(110) surface. Adsorbed CO shows attractive coupling with polarons in the surface layer, and repulsive interaction with polarons in the subsurface layer. As a result, CO adsorption depends on the reduction state of the sample. For slightly reduced surfaces, many adsorption configurations with comparable adsorption energies exist and polarons reside in the subsurface layer. At strongly reduced surfaces, two adsorption configurations dominante: either inside an oxygen vacancy, or at surface Ti$_{5c}$ sites, coupled with a surface polaron

Modeling polarons in density functional theory: lessons learned from TiO2

Density functional theory (DFT) is nowadays one of the most broadly used and successful techniques to study the properties of polarons and their effects in materials. Here, we systematically analyze the aspects of the theoretical calculations that are crucial to obtain reliable predictions in agreement with the experimental observations. We focus on rutile TiO2, a prototypical polaronic compound, and compare the formation of polarons on the (110) surface and subsurface atomic layers. As expected, the parameter U used to correct the electronic correlation in the DFT + U formalism affects the resulting charge localization, local structural distortions and electronic properties of polarons. Moreover, the polaron localization can be driven to different sites by strain: due to different local environments, surface and subsurface polarons show different responses to the applied strain, with impact on the relative energy stability. An accurate description of the properties of polarons is key to understand their impact on complex phenomena and applications: as an example, we show the effects of lattice strain on the interaction between polarons and CO adsorbates

Ordered Array of Single Au Adatoms with Remarkable Thermal Stability: Au/Fe3O4(001)

We present a Scanning Tunneling Microscopy (STM) investigation of gold deposited at the magnetite Fe3O4(001) surface at room temperature. This surface forms a reconstruction with (\surd2\times\surd2)R45{\deg} symmetry, where pairs of Fe and neighboring O ions are slightly displaced laterally, forming undulating rows with 'narrow' and 'wide' adsorption sites. At fractional monolayer coverages, single Au adatoms adsorb exclusively at the narrow sites, with no significant sintering up to annealing temperatures of 400 {\deg}C. The strong preference for this site is possibly related to charge and orbital ordering within the first subsurface layer of the reconstructed Fe3O4(001) surface. Because of their high thermal stability, the ordered Au atoms at Fe3O4(001)- (\surd2\times\surd2)R45{\deg} could provide useful for probing the chemical reactivity of single atomic species.Comment: Duplicate entry, newer version at 1205.0915. http://arxiv.org/abs/1205.091