Optical Spectroscopic Determination of Photoexcited Small-Polaron Hopping in Transition Metal Oxide Photocatalysts

Ultrafast small‐polaron formation profoundly shapes the electronic and catalytic behaviour of transition metal oxides (TMOs). Despite its significance, spectroscopic investigations of photoexcited polarons hopping in TMOs have remained unreported. Here, we present the first optical spectroscopic observation of photoexcited small-polaron hopping across the first-row TMOs, using femtosecond transient absorption spectroscopy. This polaronic feature rises within 500 fs as Drude‐type absorption converts to localized, polaronic absorption. Fitting with a small‐polaron optical conductivity model yields polaron relaxation energies of 400-650 meV, evidencing substantial energy loss upon self‐trapping. Kinetic analysis shows that oxides with open d-shell localize charge most readily: polaron formation activation barriers are low in all TMOs (0-10 meV) and reach their minimum in open d-shell systems, whereas hopping barriers remain much higher (200-350 meV). This work defines a clear spectroscopic and kinetic benchmark, highlighting the trade-off between charge localization and mobility, and the critical role of polaron formation in TMOs photocatalysts.