Polarons are a type of localized excess charge in materials and often form in transition metal oxides. The large effective mass and confined nature of polarons make them of fundamental interest for photochemical and electrochemical reactions. The most studied polaronic system is rutile TiO2 where electron addition results in small polaron formation through the reduction of Ti(IV) d0 to Ti(III) d1 centers. Using this model system, we perform a systematic analysis of the potential energy surface based on semiclassical Marcus theory parametrized from the first-principles potential energy landscape. We show that F-doped TiO2 only binds polaron weakly with effective dielectric screening after the second nearest neighbor. To tailor the polaron transport, we compare TiO2 to two metal-organic frameworks (MOFs): MIL-125 and ACM-1. The choice of MOF ligands and connectivity of the TiO6 octahedra largely vary the shape of the diabatic potential energy surface and the polaron mobility. Our models are applicable to other polaronic materials.
Bibliographical noteFunding Information:
Via our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/R029431), this work used the ARCHER2 UK National Supercomputing Service ( http://www.archer2.ac.uk ). We are also grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194 and EP/T022213).
© 2023 The Authors. Published by American Chemical Society.