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Small polaron formation limits the mobility and lifetimes of photoexcitedcarriers in metal oxides. As the ligand field strength increases, the carriermobility decreases, but the effect on the photoexcited small polaron formationis still unknown. Extreme ultraviolet transient absorption spectroscopy isemployed to measure small polaron formation rates and probabilities in goethite({\alpha}-FeOOH) crystalline nanorods at pump photon energies from 2.2 to 3.1eV. The measured polaron formation time increases with excitation photon energyfrom 70 {\pm} 10 fs at 2.2 eV to 350 {\pm} 30 fs at 2.6 eV, whereas the polaronformation probability (85 {\pm} 10%) remains constant. By comparison tohematite ({\alpha}-Fe2O3), an oxide analog, the role of ligand composition andmetal center density in small polaron formation time is discussed. This worksuggests that incorporating small changes in ligands and crystal structurecould enable the control of photoexcited small polaron formation in metaloxides.

Photoexcited Small Polaron Formation in Goethite ({\alpha}-FeOOH) Nanorods Probed by Transient Extreme Ultraviolet Spectroscopy