Interaction of molecular oxygen with semiconducting oxide surfaces plays a key role in many technologies. The topic is difficult to approach both by experiment and in theory, mainly due to multiple stable charge states, adsorption configurations, and reaction channels of adsorbed oxygen species. Here we use a combination of noncontact atomic force microscopy (AFM) and density functional theory (DFT) to resolve [Formula: see text] adsorption on the rutile [Formula: see text](110) surface, which presents a longstanding challenge in the surface chemistry of metal oxides. We show that chemically inert AFM tips terminated by an oxygen adatom provide excellent resolution of both the adsorbed species and the oxygen sublattice of the substrate. Adsorbed [Formula: see text] molecules can accept either one or two electron polarons from the surface, forming superoxo or peroxo species. The peroxo state is energetically preferred under any conditions relevant for applications. The possibility of nonintrusive imaging allows us to explain behavior related to electron/hole injection from the tip, interaction with UV light, and the effect of thermal annealing.

Center for Computational Materials Science University of Vienna 1090 Vienna Austria

Central European Institute of Technology Brno University of Technology 612 00 Brno Czech Republic

Department of Surface and Plasma Science Faculty of Mathematics and Physics Charles University 180 00 Prague 8 Czech Republic

Dipartimento di Fisica e Astronomia Università di Bologna 40127 Bologna Italy

Faculty of Physics University of Vienna 1090 Vienna Austria

Institute of Applied Physics Technische Universität Wien 1040 Vienna Austria

Institute of Applied Physics Technische Universität Wien 1040 Vienna Austria;

Institute of Physical Engineering Brno University of Technology 616 69 Brno Czech Republic

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Structure of an Ultrathin Oxide on Pt3Sn(111) Solved by Machine Learning Enhanced Global Optimization

Structure of an Ultrathin Oxide on Pt3 Sn(111) Solved by Machine Learning Enhanced Global Optimization