Electron transport in pure and substituted iron oxyhydroxides by small-polaron migration

Iron oxyhydroxides (FeOOH) are common crystalline forms of iron that play a critical role in technology and the natural environment via a variety of important reduction-oxidation reactions, including electrical semiconduction as an aspect. However, a basic understanding of the electron transport properties of these systems is still lacking. We examine the electron mobility in goethite (α-FeOOH), akaganéite (β-FeOOH), and lepidocrocite (γ-FeOOH) polymorphs by means of density functional theory based (DFT+U) calculations. We show that room temperature charge transport should be dominated by the small-polaron hopping type, and that the attendant mobility should be highest for pure goethite and akaganéite. Hopping pathways through the various lattices are discussed in terms of individual electron exchange steps and rates for each. Given the usual occurrence of compositional impurities in natural iron oxyhydroxides, we also investigate the effect of common stoichiometric defects on the electron hopping activation energies such as Al and Cr substitutional cations in goethite, and Cl anions in the channels of akaganéite