Time-Domain View of Polaron Dynamics in Metal Oxide Photocatalysts

The polaron is a fundamental physical phenomenon in transition metal oxides (TMOs), and it has been studied extensively for decades. However, the implication of a polaron on photochemistry is still ambiguous. As such, understanding the fundamental properties and controlling the dynamics of polarons at the atomistic level is desired. In this Perspective, we seek to highlight the recent advances in studying small polarons in TMOs, with a particular focus on nonadiabatic molecular dynamics at the ab initio level, and discuss the implications for photocatalysis from the aspects of the structure, intrinsic physical properties, formation, migration, and recombination of small polarons. Finally, various methods were proposed to advance our understanding of manipulating the small-polaron dynamics, and strategies to design high-performance TMO-based photoelectrodes were discussed.