Publication date: 15th May 2025
Spinel oxides containing transition metals are attractive materials for photocatalytic and photoelectrochemical applications due to their inexpensive compositions, absorption of visible light, robust chemical stability, and ability to accommodate cations with multiple oxidation states and geometries.[refs] The presence of transition metals in spinel oxides contributes partially filled, weakly dispersive 3d orbitals to the electronic band structure which are highly conducive to carrier localization and polaron formation. Spinel oxides (AB2O4) crystallize with Fd3̅m symmetry, containing two different site symmetries for metal ions (A: Td, B: Oh), which offer a unique system to assess the influence of local metal coordination on photophysical properties. Because of the presence of two coordination sites, spinel oxides can be described by an inversion parameter: 0.0 < x < 1.0. The spinel is considered “normal” when x = 0.0 and all the A cations occupy tetrahedral sites. When x = 1.0, all of the A cations occupy octahedral sites and the spinel is fully inverted. Intermediate values of x correspond to the presence of A cations in both tetrahedral and octahedral sites. This poster presentation explores the influence of local coordination geometry and cation inversion on photoinduced polaronic properties of spinel oxides containing transition metal oxides using a combined approach of resonance Raman spectroscopy, temperature-dependent optical spectroscopy and Hubbard-corrected density functional theory.
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