Interplay between adsorbates and polarons: CO on rutile TiO2(110)

M. Reticcioli, I. Sokolović, M. Schmid, U. Diebold, M. Setvin, C. Franchini

Center for Computational Materials Science, Faculty of Physics, University of Vienna, 1090 Wien, Austria
Institut für Angewandte Physik, TU Wien, 1040 Wien, Austria

Phys. Rev. Lett. 122 (2019) 016805

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 Ti5c 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.

Corresponding authors: Cesare Franchini and Martin Setvin (setvin at iap_tuwien_ac_at).

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