Interplay between Adsorbates and Polarons: CO on Rutile TiO2(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, scanning tunneling microscopy, and atomic force microscopy, we analyze the interaction of polarons with CO molecules adsorbed on the reduced rutile TiO2(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 dominate: either inside an oxygen vacancy, or at surface Ti-5c, sites, coupled with a surface polaron. Similar conclusions are predicted for TiO2(110) surfaces containing near-surface Ti interstitials. These results show that polarons are of primary importance for understanding the performance of polar semiconductors and transition metal oxides in catalysis and energy-related applications.