Ag-induced Stabilization of Multiple Surface Polarons on Perfect and Reduced TiO Rutile (110)

The recent advent of cutting-edge experimental techniques allows for a precise synthesis of subnanometer metal clusters composed of just a few atoms, opening new possibilities for subnanometer science. In this work, via first-principles modeling, we show how the decoration of perfect and reduced TiO surfaces with Ag atomic clusters enables the stabilization of multiple surface polarons. Moreover, we predict that Ag clusters are capable of promoting defect-induced polarons transfer from the subsurface to the surface sites of reduced TiO samples. For both planar and pyramidal Ag clusters, and considering four different positions of bridging oxygen vacancies, we model up to 14 polaronic structures, leading to 134 polaronic states. About 71% of these configurations encompass coexisting surface polarons. The most stable states are associated with large inter-polaron distances (>7.5 Å on average), not only due to the repulsive interaction between trapped Ti 3d electrons, but also due to the interference between their corresponding electronic polarization clouds [P. López-Caballero et al., J. Mater. Chem. A 8, 6842-6853 (2020)]. As a result, the most stable ferromagnetic and anti-ferromagnetic arrangements are energetically quasi-degenerate. However, as the average inter-polarons distance decreases, most (≥70%) of the polaronic configurations become ferromagnetic. The optical excitation of the midgap polaronic states with photon energy at the end of the visible region causes the enlargement of the polaronic wave function over the surface layer. The ability of Ag atomic clusters to stabilize multiple surface polarons and extend the optical response of TiO surfaces toward the visible region bears importance in improving their (photo-)catalytic properties and illustrates the potential of this new generation of subnanometer-sized materials.