Do Small Hole Polarons Form in Bulk Rutile TiO 2 ?

作者：Shay McBride, Wei Chen, Tanja Cuk, Geoffroy Hautier · 发表于：The Journal of Physical Chemistry Letters · 年份：2025 · DOI：10.1021/acs.jpclett.4c03078 · 被引用次数：9 · 研究领域：Electronic and Structural Properties of Oxides、Copper-based nanomaterials and applications、Advanced Condensed Matter Physics

Hole transport and localization through small polarons are essential to the performance of TiO 2 in photocatalysis applications. The existence of small hole polarons in bulk rutile TiO 2 has been, however, controversial with contradicting evidence from theory and experiments. Here, we use first-principles computations and more specifically a Koopmans’ compliant hybrid functional and charge correction to study small hole polarons in bulk rutile. We find that a fraction of exchange exists, satisfying Koopmans’ compliance for the polaron state and reproducing the band gap provided that charge correction is used. We clearly show that first-principles computations indicate that the small hole polaron is only slightly stable, with a formation energy tens of millielectronvolts below that of the delocalized state in bulk for rutile and more stable for anatase TiO 2 .