Chemical Modification of Polaronic States in Anatase TiO(2)(101)

[Image: see text] Two polymorphs of TiO(2), anatase and rutile, are employed in photocatalytic applications. It is broadly accepted that anatase is the more catalytically active and subsequently finds wider commercial use. In this work, we focus on the Ti(3+) polaronic states of anatase TiO(2)(101), which lie at ∼1.0 eV binding energy and are known to increase catalytic performance. Using UV-photoemission and two-photon photoemission spectroscopies, we demonstrate the capability to tune the excited state resonance of polarons by controlling the chemical environment. Anatase TiO(2)(101) contains subsurface polarons which undergo sub-band-gap photoexcitation to states ∼2.0 eV above the Fermi level. Formic acid adsorption dramatically influences the polaronic states, increasing the binding energy by ∼0.3 eV. Moreover, the photoexcitation oscillator strength changes significantly, resonating with states ∼3.0 eV above the Fermi level. We show that this behavior is likely due to the surface migration of subsurface oxygen vacancies.